PRODUCTION OF BIOFUEL BY HYDROCONVERSION OF WASTE...
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PRODUCTION OF BIOFUEL BY HYDROCONVERSION OF WASTE VIRGIN COCONUT OIL OVER HZSM-5 ZEOLITE BY MISS PANADDA YOTSOMNUK A THESIS SUBMITTED IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF MASTER DEGREE OF ENGINEERING (CHEMICAL ENGNEERING) DEPARTMENT OF CHEMICAL ENGINEERING FACULTY OF ENGINEERING THAMMASAT UNIVERSITY ACADEMIC YEAR 2017 COPYRIGHT OF THAMMASAT UNIVERSITY Ref. code: 25605810030592YLH
Transcript of PRODUCTION OF BIOFUEL BY HYDROCONVERSION OF WASTE...
PRODUCTION OF BIOFUEL BY HYDROCONVERSION OF WASTE VIRGIN COCONUT OIL OVER HZSM-5 ZEOLITE
BY
MISS PANADDA YOTSOMNUK
A THESIS SUBMITTED IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF MASTER DEGREE OF ENGINEERING
(CHEMICAL ENGNEERING) DEPARTMENT OF CHEMICAL ENGINEERING FACULTY OF ENGINEERING
THAMMASAT UNIVERSITY ACADEMIC YEAR 2017
COPYRIGHT OF THAMMASAT UNIVERSITY
Ref. code: 25605810030592YLH
PRODUCTION OF BIOFUEL BY HYDROCONVERSION OF WASTE VIRGIN COCONUT OIL OVER HZSM-5 ZEOLITE
BY
MISS PANADDA YOTSOMNUK
A THESIS SUBMITTED IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF MASTER DEGREE OF ENGINEERING
(CHEMICAL ENGINEERING) DEPARTMENT OF CHEMICAL ENGINEERING FACULTY OF ENGINEERING
THAMMASAT UNIVERSITY ACADEMIC YEAR 2017
COPYRIGHT OF THAMMASAT UNIVERSITY
Ref. code: 25605810030592YLH
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Thesis Title PRODUCTION OF BIOFUEL BY
HYDROCONVERSION OF WASTE VIRGIN
COCONUT OIL OVER HZSM-5 ZEOLITE
Author Miss Panadda Yotsomnuk
Degree Master of Engineering
Major Field/Faculty/University Chemical Engineering
Faculty of Engineering
Thammasat University
Thesis Advisor Associate Professor Wanwisa Skolpap, Ph.D.
Academic Years 2017
ABSTRACT
This research aimed to determine the influence of process parameters on
yields of biofuel production by hydroconversion of waste virgin coconut oil using
HZSM-5 zeolite catalyst and to determine statistical relationship of biofuel yields with
the operating parameters program by Pearson’s correlation. The hypothesis of this
research was tested at 95% confidence level. The various operating parameters in
batch reactor were a reaction temperature (350-400°C), an initial hydrogen pressure
(20-40 bar), and a reaction time (1-3 h). The reaction products were then separated by
distillation. The highest yields of gasoline (6.79 wt%) and kerosene (31.38 wt%) were
achieved under a temperature at 400°C, initial hydrogen pressure at 40 bar, and a
reaction time of 3 h. The highest yield of diesel of 58.62 wt% was achieved at a reaction
time of 1 h under temperature 400°C and initial hydrogen pressure 40 bar. The
experimental data were analyzed by input-output model with the coefficient of
determination (R2) of yield prediction ranging from 0.86 to 0.92. The Pearson’s
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correlation coefficients show strong dependence of reaction temperature and time on
hydrocarbon chains of various length. Yields of shorter hydrocarbon chains such as
biogasoline and biokerosene required higher reaction temperature and longer reaction
time and vice versa. Pressure dependence on yields of biofuels was insignificant.
Keywords: Virgin coconut oil, Zeolite, HZSM-5, Hydroconversion
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หวขอวทยานพนธ การผลตเชอเพลงเหลวดวยกระบวนการไฮโดรคอนเวอรชนจากการแปรรปของเสยจากกระบวนการผลตนามนมะพราวบรสทธโดยอาศยตวเรงปฏกรยาซโอไลต HZSM-5
ชอผเขยน นางสาวปนดดา ยศสมนก ชอปรญญา วศวกรรมศาสตรมหาบณฑต สาขาวชา/คณะ/มหาวทยาลย วศวกรรมเคม
วศวกรรมศาสตร มหาวทยาลยธรรมศาสตร
อาจารยทปรกษาวทยานพนธ รองศาสตราจารย ดร. วนวสาข สกลภาพ ปการศกษา 2560
บทคดยอ
งานวจยนมวตถประสงคเพอศกษาอทธพลตวแปรกระบวนการไฮโดรคอนเวอรชนโดยใชตวเรงปฏกรยาซโอไลต HZSM-5ทมตอคาผลไดในการผลตเชอเพลงชวภาพจากนามนเหลอทงจากกระบวนการผลตนามนมะพราวบรสทธ และเพอหาความสมพนธเชงสถตระหวางคาผลไดและตวแปรศกษาดวยสหสมพนธของเ พยรสน (Pearson’s correlation) ตวแปรกระบวนการท ศ กษากระบวนการไฮโดรคอนเวอรชนในเครองปฏกรณชวภาพตนแบบขนาดเลก แบบกะ ไดแกอณหภมในการทาปฏกรยาไฮโดรคอนเวอรชนท 350-400 องศาเซลเซยส, ความดนไฮโดรเจนเรมตนท 20-40 บาร และเวลาในการทาปฏกรยาท 1-3 ชวโมง ผลตภณฑเชอเพลงชวภาพในสวนของของเหลวถกวเคราะหโดยการกลน จากผลการทดลองพบวา ผลผลตสงสดของนามนไบโอเคโรซนและนามนไบโอแกสโซลนสงสดท 31.38 เปอรเซนตโดยนาหนก และ 6.79 เปอรเซนตโดยนาหนก ตามลาดบ ภายใตสภาวะอณหภม 400 องศาเซลเซยส ความดนไฮโดรเจนเรมตนท 40 บารและเวลาในการทาปฏกรยา 180 นาท และผลผลตสงสดของนามนดเซลอยท 58.62 รอยละโดยนาหนก ทอณหภม 350 องศาเซลเซยส ความดนไฮโดรเจนเรมตนท 40 บารและเวลาในการทาปฏกรยา 60 นาท จากนนทดสอบเปรยบเทยบความสมพนธระหวางผลตภณฑเชอเพลงชวภาพกบตวแปรตางๆทไดทาการศกษา โดยวเคราะหเชงสถตเพอหาคาสมประสทธสหสมพนธของเพยรสน (Pearson’s correlation) จากเมอวเคราะหขอมลการทดลองโดยใชแบบจาลองทางคณตศาสตรแบบอนพด -เอาทพต พบวาคาสมประสทธการตดสนใจ (Coefficient of determination, R2) อยในชวง 0.86-0.92 สาหรบการ
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วเคราะหเชงสถตระหวางคาผลไดและตวแปรศกษาดวยสหสมพนธของเพยรสน (Pearson’s correlation) โดยกาหนดระดบความเชอมนทรอยละ 95 พบวาความสมพนธระหวางความยาวทแตกตางกนของสายไฮโดรคารบอนทผลตได ขนกบอณหภมและระยะเวลาในการทาปฎกร ยาไฮโดรคอนเวอรชน กลาวคอ ผลตภณฑในชวงคารบอนสายโซสน เชน นามนไบโอแกสโซลนและนามนไบโอเคโรซน ใหคาผลไดสงทอณหภมสงและระยะเวลาในการเกดปฎกรยาทนาน สาหรบอทธพลความดนไฮโดรเจนไมมผลตอคาผลไดของผลตภณฑนามนเชอเพลงอยางมนยสาคญ ค ำส ำคญ: นามนมะพราวสกดเยน, ซโอไลต, HZSM-5, ไฮโดรคอนเวอรชน
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ACKNOWLEDGEMENTS
This thesis would have been impossible without the help from my advisor,
Assoc. Prof. Dr. Wanwisa Skolpap. Apart from academic support, Assoc. Prof. Dr.
Wanwisa Skolpap gave significant advice for improving my research skill. Furthermore,
she taugh me the way to live as my parents did, and gave me the education
opportunity including financial support during my study.
Besides, I would like to express my thanks to the committee including
Assoc. Prof. Dr. Nurak Grisadanurak, Assoc. Prof. Dr. Attasak Jaree, Asst. Prof. Dr.
Suwadee Kongparakul for valuable recommendations to improve quality of my thesis.
Moreover, I am deeply grateful to my family for encouragement and their
continued prayer and moral support through the course of my graduate studies. Many
thanks also for all my friends who are always very helpful and supporting.
Finally, I would like to thank Faculty of Engineering, Thammasat University
for the scholarship and gratefully acknowledge the financial support provided by
Thammasat University Research Fund
Miss Panadda Yotsomnuk
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TABLE OF CONTENTS
Page
ABSTRACT (1)
ACKNOWLEDGEMENTS (5)
LIST OF TABLES (10)
LIST OF FIGURES (13)
CHAPTER 1 INTRODUCTION 1
1.1 Background 1
1.2 Objectives 3
1.3 Scope 3
1.4 Expected output 4
CHAPTER 2 LITERATURE REVIEW 5
2.1 Vegetable oil 5
2.1.1 Coconut oil 8
2.1.2 Virgin coconut oil 9
2.2 Hydrocracking 11
2.2.1 Hydrocracking catalyst 13
2.3 Zeolite 13
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2.3.1 The structure of zeolite 14
2.3.2 Shape selectivity 16
2.3.3 ZSM-5 17
2.4 Parameter condition
2.4.1 Effect of initial hydrogen pressure
2.4.2 Effect of reaction temperature
2.4.3 Effect of reaction time
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CHAPTER 3 RESEARCH METHODOLOGY 28
3.1 Chemical and reagents 28
3.2 Methodology 31
3.2.1 Preparation of HZSM-5 zeolite 32
3.2.2 Characterization of zeolite 32
3.2.2.1 X-ray powder diffraction 32
3.2.2.2 Scanning electron microscopy 33
3.2.2.3 Temperature programmed desorption 33
3.2.2.4 Gas Chromatography-Mass Spectrometry 33
3.3 Hydrocracking process 33
CHAPTER 4 RESULTS AND DISCUSSION 37
4.1 Characterization Analysis 37
4.1.1 X-ray powder diffraction 37
4.1.2 Scanning electron microscopy 38
4.1.3 Temperature programmed desorption 40
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4.2 Effect of operating parameters on hydrocracking of waste
virgin coconut oil
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4.2.1 Effect of initial hydrogen pressure 40
4.2.2 Effect of reaction temperature 43
4.2.3 Effect of reaction time 45
4.3 Data analysis from the input-output model 48
4.4 Accuracy of models used in liquid biofuel yield prediction
4.5 Data analysis – Pearson’s correlation coefficient
4.6 The reaction product distribution
4.6.1 The number of carbon atom
4.6.2 Selectivity of kerosene range hydrocarbon
4.7 Degree of deoxygenation (DOD) and degree of cracking (DOC)
4.7.1 Effect of reaction parameters on the degree of
deoxygenation (DOD) and degree of cracking (DOC) in the
batch reactor
4.8 Continuous process
4.8.1 Experimental
4.8.2 Product Analysis
4.8.3 Effect of hydrogen flow rate
4.8.4 Effect of reaction time on catalyst activity and selectivity
to product
CHAPTER 5 CONCLUSIONS AND RECOMMENDATIONS
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5.1 Conclusion 72
5.2 Recommendations 73
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REFERENCES 74
APPENDICES 83
APPENDIX A Raw data of characterization
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APPENDIX B Raw data of experimental results 92
APPENDIX C Calculation
APPENDIX D Pearson’s correlation
APPENDIX E Product distribution (batch reactor)
APPENDIX F The product distribution was detected by gas
chromatography (continuous reactor)
APPENDIX G The pathway of hydroprocessing process (batch process)
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BIOGRAPHY 110
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LIST OF TABLES
Tables Page
2.1 The composition of fatty acid in various types of vegetable oils
(%w/w)
6
2.2 Free fatty acid (FFA) I virgin coconut oil 10
2.3 Previous studies on the effect of initial hydrogen pressure 23
2.4 Previous studies on the effect of reaction temperature 26
2.5 Previous studies on the effect of reaction time
3.1 Analysis data of low-grade waste virgin coconut oil (WCO)
3.2 Analysis data of high-grade waste virgin coconut oil (WCO)
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4.1 Results of TPD-NH3 analysis over HZSM-5 zeolite 40
4.2 The effect of initial hydrogen pressure on conversion (Xl), yield,
and selectivity of liquid product fraction for waste virgin coconut
oil
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4.3 The effect of reaction temperature on conversion (Xl), yield, and
selectivity of liquid product fraction for waste virgin coconut oil
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4.4 The effect of reaction time on conversion (Xl), yield, and
selectivity of liquid product fraction for waste virgin coconut oil
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4.5 The calculated correlation coefficients
4.6 Pearson’s correlation coefficients of yield of liquid biofuel with
initial hydrogen pressure (P), reaction temperature (T), and
reaction time (t)
A.1 Compositional analysis of low-grade waste virgin coconut oil
A.2 Compositional analysis of high-grade waste virgin coconut oil
A.3 Data of Theta and six highest peaks of zeolite and H-zeolite
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A.4 Raw data of temperature programmed desorption of ammonia
A.5 Flash point analysis
B.1 Experimental conditions
B.2 Effect of initial hydrogen pressure on product yield, selectivity
and conversion of waste virgin coconut oil cracking to biofuels
through hydrocracking process over HZSM-5 as catalyst at 400°C
and 1 h
B.3 Effect of reaction temperature on product yield, selectivity and
conversion of waste virgin coconut oil cracking to biofuels
through hydrocracking process over HZSM-5 as catalyst at 40 bar
and 1 h
B.4 Effect of reaction time on product yield, selectivity and
conversion of waste virgin coconut oil cracking to biofuels
through hydrocracking process over HZSM-5 as catalyst at 400°C
and 40 bar
D.1 Pearson’s correlation for operating parameters on gasoline
production
D.2 Pearson’s correlation for operating parameters on kerosene
production
D.3 Pearson’s correlation for operating parameters on diesel
production
D.4 Liquid biofuel yield comparison between experimental (actual)
and model predicted result
E.1 The effect of initial hydrogen pressure on the product
distribution and degree of deoxygenation and degree of cracking
E.2 The effect of reaction temperature on the product distribution
and degree of deoxygenation and degree of cracking
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E.3 The effect of reaction time on the product distribution and
degree of deoxygenation and degree of cracking
E.4 The product distribution and degree of deoxygenation and
degree of cracking at the condition no add catalyst (400°C/40
bar/60 minutes) and no add hydrogen (400°C/60 minutes)
E.5 The selectivity of carbon atom number of liquid yield from
hydrocracking process over HZSM-5 was detected by gas-
chromatography
E.6 The distribution of aromatic, alkane, and alkene for kerosene
fraction
F The effect of hydrogen flow rate (ml/min) on the selectivity to
product at the various of reaction time (°C)
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LIST OF FIGURES
Figures Page
2.1 Chemical structure of vegetable oil 7
2.2 Coconut palm 8
2.3 Virgin coconut oil 9
2.4 The possible reaction pathways 12
2.5 Structure of zeolite 14
2.6 Various types of zeolite; (a) small pore zeolites, (b) medium
pore zeolites, (c) large pore zeolites
15
2.7 Shape selectivity in zeolite channels 16
2.8 Scheme of the channel system in ZSM-5 17
2.9 Scheme for generating Bronsted and Lewis acid sites in zeolites
3.1 low-grade and high-grade waste virgin coconut oil
3.2 Experimental procedure
3.3 Scheme of HZSM-5 zeolite preparation
3.4 Schematic diagram of the batch reactor
3.5 Batch reactor
3.6 Distillation
4.1 XRD patterns of HZSM-5
4.2 SEM images of (a) (b) HZSM-5
4.3 SEM images of (c) (d) ZSM-5
4.4 EDX Spectrum
4.5 Effect of initial hydrogen pressure on liquid product fractions
(wt%) in the catalytic hydrocracking of waste virgin coconut oil
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(Conditions: Catalyst = 1 g of HZSM-5, reaction temperature =
400°C and reaction period = 1 h)
4.6 Effect of reaction temperature on liquid product fractions (wt%)
in the catalytic hydrocracking of waste virgin coconut oil
(Conditions: Catalyst = 1 g of HZSM-5, initial hydrogen pressure
= 40 bar and reaction period = 1 h)
4.7 Effect of reaction time on liquid product fractions (wt%) in the
catalytic hydrocracking of waste virgin coconut oil (Conditions:
Catalyst = 1 g of HZSM-5, initial hydrogen pressure = 40 bar and
reaction temperature = 400°C)
4.8 The input-output correlation of the effect of initial hydrogen
pressure (P)
4.9 The input-output correlation of the effect of reaction
temperature(T)
4.10 The input-output correlation of the effect of reaction time (t)
4.11 Correlation between actual and predicted yield for gasoline
4.12 Correlation between actual and predicted yield for kerosene
4.13 Correlation between actual and predicted yield for diesel
4.14 The effect of initial hydrogen pressure on the distribution of
carbon atom number of liquid products yielded from
hydrocracking process over HZSM-5
4.15 The effect of reaction temperature on the distribution of carbon
atom number of liquid products yielded from hydrocracking
process over HZSM-5
4.16 The effect of reaction time on the distribution of carbon atom
number of liquid products yielded from hydrocracking process
over HZSM-5
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4.17 The effect of reaction temperature on the selectivity for kerosene
fraction toward formation of aromatic, alkane, and alkene
4.18 The effect of initial hydrogen pressure on the selectivity for
kerosene fraction toward formation of aromatic, alkane, and
alkene
4.19 The effect of reaction time on the selectivity for kerosene fraction
toward formation of aromatic, alkane, and alkene
4.20 The effect of the reaction temperature on the degree of
deoxygenation on over HZSM-5 catalysts
4.21 The effect of the reaction temperature on the degree of cracking
on over HZSM-5 catalysts
4.22 The effect of the initial hydrogen pressure on the degree of
deoxygenation on over HZSM-5 catalysts
4.23 The effect of the initial hydrogen pressure on the degree of
cracking on over HZSM-5 catalysts
4.24 The effect of the reaction time on the degree of deoxygenation
on over HZSM-5 catalysts
4.25 The effect of the reaction time on the degree of cracking on over
HZSM-5 catalysts
4.26 Reactor set-up
4.27 Decanoic acid conversion over HZSM-5 as function of time
4.28 The effect of the hydrogen flow rate on product formation at
the reaction time 30 minutes
4.29 The effect of the hydrogen flow rate on product formation at
the reaction time 60 minutes
4.30 The effect of the hydrogen flow rate on product formation at
the reaction time 90 minutes
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4.31 The effect of a reaction time with the hydrogen flow rate 50
ml/min
4.32 The effect of hydrogen flow rate on the selectivity to product at
30 minutes
4.33 The effect of hydrogen flow rate on the selectivity to product at
60 minutes
4.34 The effect of hydrogen flow rate on the selectivity to product at
90 minutes
A.1 NH3-TPD of HZSM-5
A.2 The pathway reaction of hydroprocessing of tetradecanoic acid
A.3 The pathway reaction of hydroprocessing of dodecanoic acid
A.4 The pathway reaction of hydroprocessing of decanoic acid
A.5 The pathway reaction of hydroprocessing of octanoic acid
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CHAPTER 1 INTRODUCTION
This chapter presents background, objectives, scope and expected outcomes of this work.
1.1 Background
Due to worldwide environmental concern and the increasing fuel demand,
this energy source is being steadily substituted by available renewable sources of liquid
fuels such as biofuels, alcohols and vegetable oil. The transformation of vegetable oil
to biofuel offers environmental benefits since they are renewable, available, low sulfur
and aromatics and bio-degradable. Similar to fossil fuel derived from petroleum,
vegetable oil is possible to be thermochemically converted to biofuels such as
unfinished gasoline, kerosene, and biodiesel (Kimura et al., 2016; Zandonai et al., 2016).
There have been many researches about biodiesel production by either the
transesterification of vegetable oils and animal fats or by the esterification of refined
fatty acid esters. The vegetable oils transesterification with short-chain alcohols is
carried out by acid or basic catalysts while the esterification of free fatty acids (FFA)
present in animal fats with alcohols is carried out over heterogeneous acid catalysts
(Kappally et al., 2015). As a result, the products derived from these syntheses are
glycerol and esters of the renewable fuel or so-called biodiesel. The selection criteria
of feedstock type depends on its domestic availability, cost and quality. Based on the
domestic feedstock yield per harvest areas, palm oil and coconuts have the first and
second highest potential as precursor for biodiesel production, respectively
(Nimmanterdwong et al., 2015). Hence, waste virgin coconut oil with high fatty acid
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content (Oliveira et al., 2010) a possible alternative biofuel feedstock, is available at
no-to-low price and does not have niche applications.
World energy consumed by transportation sector has been substantially
increased higher than industry and household (Yilmaz et al., 2017). The transportation
energy consumption projected for 2020 will be 74% of total petroleum-based energy.
The aviation section, a major transportation subsector, depends on fossil fuels
contributing to atmospheric pollution. Numerous researches have been conducted to
develop sustainable alternatives derived from biomass for aviation (Neuling et al.,
2018).
Biofuel, renewable energy, can replace commercial petroleum-based
products. In recent years, many researchers have focused on development of the
hydrocarbons production from biomass such as clean gasoline, kerosene, and diesel
to reduce environmental problems (Kimura et al., 2013; Zhao et al., 2015). Vegetable
oils or animal fats, as an organic matter, is mostly used as biofuel cropsuch as
sunflower (Rasyid et al., 2015; Zandonai et al,, 2016), coconut (Charusiri et al,, 2006;
Anad et al., 2016), castor (Nasikin et al., 2009), soybean (Sotel-boyas et al., 2008),
canola, cotton (Sotel-boyas et al., 2011), Jatropha curcas (Hanafi et al., 2015), and palm
oil (Sirajudin et al., 2013; Chang et al., 2013). The use of vegetable oils for biofuel
production offers benefits because they are renewable, readily available, low aromatic
and sulfur content and bio-degradable. Moreover, byproducts of esterification and
transesterification processes are glycerol which is precursor for soap manufacturing.
Due to high viscosity and oxygen content and poor atomization and lubricity of various
oils derived from plants and animals can be used as in engine with modification to
meet strict fuel quality. The feedstock choice depends on its availability, and cost.
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Coconut oil extracted from fresh mature kernel of coconut is known as
virgin coconut oil (VCO). Nowadays, (VCO) has gain a lot of public attention in the
scientific research. The extraction process of VCO is obtained by either mechanical or
natural means without applying heat, chemical refining, bleaching or deodorizing to
avoid deteriorating oil quality.
In the production process of virgin coconut oil, abundant waste oils
contains free fatty acid (FFA) similar to the FFA in crude coconut oil are generated. The
low quality waste virgin coconut oil are potential feedstock for bio-oil production.
1.2 Objectives
Due to high FFA content of abundant waste virgin coconut oils, this study
aimed to synthesize ZSM-5 zeolite catalyst for hydrocracking of biofuel production
such as gasoline, kerosene, and diesel.
The objectives are listed as follows:
i. To determine the effect of hydrocracking conditions such as temperature,
pressure, and reaction time on yields of gasoline, biodiesel and kerosene.
ii. To find optimal preparation condition for biofuel production using modified
ZSM-5.
iii. To develop input-output model for predicting yields of gasoline, biodiesel and
kerosene in catalytic hydro-treating.
1.3 Scope
Waste virgin coconut oils, potential feedstock, are converted to biofuels
such as gasoline, biodiesel and kerosene by modified ZSM-5 catalysts. Generally, the
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rate of cracking and the final product depend on the temperature, pressure, and
presence of catalysts. Activity of catalysts was investigated in hydrocracking of waste
virgin coconut oil in a high-pressure reactor system using hydrogen gas.
The reaction temperature for hydrocracking experiments were in a range
of 350 to 400°C, initial hydrogen pressure between 20 and 40 bar, and reaction period
varied between 1 and 3 h. The production of biofuel under the different conditions
was then analyzed by distillation. The yield, conversion and selectivity of each biofuel
type produced were estimated and predicted by an input-output model.
1.4 Expected output
1. Value-added conversion of waste virgin coconut oil is achieved towards
zero waste generation.
2. An input-output model is developed to predict yields of biofuels at
various temperature, initial hydrogen pressure, and reaction period.
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CHAPTER 2
LITERATURE REVIEW
This chapter describes theory and background related to indirect and direct
hydrocracking process and the treatment of zeolite catalyst involved. The effect of
parameters such as the reaction temperature, initial hydrogen pressure, and reaction
time on products yield.
2.1 Vegetable oil
A vegetable oil containing triglyceride is extracted from fruits or seeds of
plants such as olive, soybean, coconut, corn, peanuts, cotton seed and palm nuts. Like
other plants, oil crops use sunlight and photosynthesis for their growth and eliminate
carbon dioxide (CO2) from the Earth’s atmosphere. During a combustion of engine,
carbon dioxide is exhausted. Then the oil crops consume carbon dioxide emitted in
the atmosphere resulting in reducing amount of greenhouse gas emission. Nowadays,
there is a limit availability of fossil fuel resources, i.e., natural gas, petroleum and coal.
Therefore, fossil fuels cannot replenish rapidly to satisfy the growing energy demand
resulting in development of renewable energy derived from natural sources such as
wind, solar, hydro, tide and biomass which can be used as fossil fuel substitute.
Especially, the use of vegetable oils as alternative sources is increasingly interesting for
many reasons, such as environmentally friendly, sustainable sources, and low
production cost. Hydrocarbons produced by vegetable oils such as coconut oil (Kimura
et al., 2013), sunflower oil (Zhao et al., 2015), soybean oil (Ishihara et al., 2014;
Zandonai et al., 2016), jatropha oil (Anand et al., 2016), palm oil (Siregar et al., 2005,
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Budianto et al., 2014), Calophyllum inophyllum oil (Hafshan et al., 2017), Sunan
candlenut oil (Muhammad et al., 2017) and rapeseed oil (Simacek et al., 2009).
The various types of renewable energy sources mostly depend on regional
climate conditions. For example, research using canola oil and coconut oil have been
served as industrial raw materials in biofuel conversion processes in Canada (Adjaye &
Bakhshi, 1995; Idem et al., 1997) and in Philippines (Arida et al., 1986), respectively.
Palm oil has been widely used as the renewable energy source in Malaysia, where is
the largest producer of palm oil in the world (Salam et al., 1996; Mahmud, 1998, Bhatia
et al., 1998, Twaiq et al., 1999). Generally, most vegetable oils contain fatty acids
whose carbon numbers ranging from C14 to C20 while the fatty acid composition of
coconut oil ranges from C6 to C20 as presented in Table 2.1.
Table 2.1
The composition of fatty acid in various types of vegetable oils (Mueller, 2013)
Type of oil Composition (%w/w)
caproic acid
caprylic acid
capric acid
lauric acid
myristic acid
palmitic acid
stearic acid
arachidic acid
Coconut 0.04±0.2 7±2.0 8±2.0 48±4 16±3.0 9.2±1.5 2±1.0 0.25±0.2
Corn 4±0.8 7±1.2 0.6±0.4 10±2 3.5±1.5
Cottonseed 0.4±0.2 20±2.5 2±0.6
Palm kernel 4±1 5±2 41±5 16±2 8±1.0 2±0.8
Olive 0.65±0.
2 11.5±4 2±0.5 0.22±0.12
Soybean 0.5±0.2 9±2 4±1.5
Sunflower 3.7±1.5 2±0.8 2.3±1.2
Peanut 7.5±1.5 4.5±1.8 3±1.2
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The chemical structure of triglyceride vegetable oil extracted from a variety
of plants is shown in Figure 2.1. Fatty acid chains vary in lengths, measured as the
number of C-molecules in the chain, and saturation. Saturations are no “missing” H-
molecules in the fatty acid chain.
Figure 2.1 Chemical structure of vegetable oil (Dutton, 2018)
Several researchers have been conducted the hydrocracking process that
can crack vegetable oils into biofuel products. Marlinda et al. (2016) obtained the
highest yield of gas oil derived from Cerbera manghas oil about 46.45% by using Co-
Ni/HZSM-5 catalyst under hydrogen initial pressure of 15 bar in a batch reactor. The
conversion of Calophyllum inophyllum oil into liquid biofuel has reported by Rasyid
et al. (2015). The hydrocracking process was operated at 350°C and 30 bar with non-
sulfide CoMo catalyst. The yields of biofuel were 25.63 wt% gasoline, 17.31 wt%
kerosene, and 38.59 wt% diesel with CoMo/γ-Al2O3 catalyst. Moreover, CoMo/ γ-Al2O3
catalyst provides higher conversion than CoMo/SiO2 and CoMo/γ-Al2O3-SiO2. When
comparing a various vegetable oils, i.e., palm oil, soybean oil, and canola oil, the
biofuel production from the palm oil produces more liquid products and light C2-C4
olefins than soybean oil and canola oil (Mustafa et al., 2012).
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2.1.1 Coconut oil
The tropical countries have used coconut from the tree Cocos
nucifera, Family Aracaceae (palm family) for thousands of years (Kappally et al., 2015).
The production of coconuts is mostly in South Asia, such as India, the Philippines,
Thailand and Indonesia. Coconut oil or copra oil, is actually an extracted from the
kernel or meat of mature coconuts of coconut palm (Cocos nucifera) with many
applications. All parts of the coconut tree such as meat, water, husk shell, wood, and
leaves are useful in terms of significant economic value, therefore coconut palm is
commonly known as the "Tree of Life" (Gervajio, 2005).
Figure 2.2 Coconut palm Information Nigeria. (2016). Retrieved from
http://www.informationng.com
Coconut oil usually has the composition of the fatty acids between
twelve carbons and twenty carbons. Lauric acid (12:0) content, about 45–56% of the
coconut oil fatty acid compositions, is the major component; however, a variation of
fatty acid contents in coconut oil depends on the coconut variety as shown in Table
2.1.
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2.1.2 Virgin coconut oil
Generally, clear or colourless virgin coconut oil (VCO) is the purest
form of coconut oil and directly extracted from fresh coconut kernel by either
mechanical or natural means, with or without the use of heat, and no chemical refining,
bleaching or deodorization (Villarino et al., 2007). Due to the powerful antimicrobial
and antiviral properties of virgin coconut oil bearing significant amount of short to
medium-chain fatty acids and natural vitamin E, this drives the global increase of VCO
demand in manufacturing pharmaceutical, natural food and cosmetics products.
Figure 2.3 Virgin coconut oil Roxas Sigma Agriventures, Inc. (2016). Retrieved from
http://www.roxassigmaagri.com
Other types of edible coconut oil is refined, bleached and
deodorised coconut oil (RBD) which is derived from copra. The dried coconut kernel
can be achieved by the processes of sun drying, smoke drying or hot air drying. Refined,
bleached and deodorised coconut oil (RBD) and VCO have the same physical and
chemical characteristics, but have different sensory attributes and prices. Free fatty
acid (FFA) content in VCO and palm oil contain high content of saturated fatty acids
as shown in Table 2.2, so it is possible to be transformed to more valuable
hydrocarbon such as biofuel for vehicle and bio-LPG (Liu et al., 2012).
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Table 2.2
Free fatty acid (FFA) in virgin coconut oil (Dayrit et al., 2011)
Free fatty acid % FFA composition
caproic (C6:0) 0.24-0.56
caprylic (C8:0) 4.15-9.23
capric (C10:0) 4.27-6.08
lauric (C12:0) 46.0-52.6
myristic (C14:0) 16.0-19.7
palmitic (C16:0) 7.65-10.1
stearic (C18:0) 2.73-4.63
oleic (C18:1) 5.93-8.53
linoleic (C18:2) 1.00-2.03
Hydrocracking reaction of coconut oil into gasoline fraction has been
performed using mesoporous Ni/modified natural zeolite catalyst at various
temperatures (Salim et al., 2016). After GC-MS analysis of liquid organic product, it
indicates that the hydrocracking of coconut oil involves disconnection (cracking) of C-
C bonding, hydrogenation, isomerization, cyclization and deoxygenation. A variation of
distribution of yields depends on catalytic reaction with a various of temperatures. At
temperature of 450°C the highest conversion of coconut oil to gasoline fraction (C7-
C12), diesel fraction (C13-C18), and heavy fraction (>C18) were 11.73 wt%, 4.82 wt%,
and 15.07 wt% respectively.
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2.2 Hydrocracking
There are several conversion methods of vegetable oils to biofuels such
as transesterification, thermal cracking, catalytic cracking, and hydrocracking (Zhao et
al., 2015; Rasyid et al., 2015; Zandonai et al., 2016; Charusiri et al., 2006; Anad et al.,
2016). Transesterification of triglycerides containing vegetable oils with an alcohol
(methanol or ethanol) in the presence of catalyst is a decomposition of glycerin-fatty
acid linkages into glycerol and esters of biofuel (Kappally et al., 2015). As a result the
product derived from this synthesis process is biodiesel. Thermal cracking process is
usually used to crack heavy hydrocarbons of vegetable oil into lighter hydrocarbons
as biofuel by thermolysis under high temperature, high pressure without catalyst. If the
product residence time in the reactor is so long that the overcracking of hydrocarbon
conversion products takes place, (Salim et al., 2016; Verma et al., 2015). Therefore, the
development of thermal cracking process for producing middle distillates has been
limited. Similarly, a catalytic cracking method can transform vegetable oil as raw
material into biofuel under high pressure of hydrogen causing formation of coke on
the catalyst and olefinic and aromatic compound in products.
In the 1980’s many researches has attempted to shorten the long chain
hydrocarbons of vegetable oils to produce gasoline, kerosene, and diesel.
Hydrocracking is a process that combines between catalytic cracking and
hydrogenation together to produce more desirable products. The process needs high
temperature (300 - 400˚C), high pressure, and catalytic activity. More energy also needs
to crack vegetable oils into hydrocarbons to produce more desirable products.
However, the properties of products such as oxidation stability increased and cetane
numbers are improved by hydrocracking process (Can et al., 2012). The reduction of
biofuel production cost and the improvement of product yield can be achieved by
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development of good selectivity and long lifetime catalysts. The two functions of
catalyst are acidic function and metallic function. The acidic sites provide for the
cracking and isomerization, while the metallic sites as the metals loaded of the support
provide for the hydrogenation. High acidity tends to cause coke on the surface of
catalyst, which leads to deactivation. A good balance between the two functions has
to be maintained for a suitable hydrocracking catalyst. Moreover, the properties of the
products by hydrocracking process are considerably better more than by the
transesterification (Salwa et al., 2015).
Figure 2.4 The possible reaction pathways (Kim et al., 2014 and Veriansyah et al., 2012)
The possible pathways consist of a series of reactions that take place during
hydroprocessing as illustrated in Figure 2.4. During hydroprocessing, double bonds that
contain in triglycerides, it becomes saturated triglycerides at high temperature
hydrogen. The resulting free fatty acid and propane occur, when the saturated
triglycerides are continuously cracked. The production of straight-chain alkanes can be
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occurred through hydrodeoxygenation, decarbonylation, or decarboxylation. Oxygen
removal in the form of water is achieved by saturation of C=O, followed by breaking
of C-O and C-C bonds during hydrodeoxygenation (Bezergianni et al., 2015), while
carbon dioxide (CO2) and carbon monoxide (CO) are produced during decarboxylation
and decarbonylation, respectively (Mohammad et al., 2013). The quantity of resulting
products can be transformed into isomers, aromatics, light hydrocarbons and cyclo-
compounds that depend on the operating parameters and types of catalysts (Kim et
al., 2014; Mohammad et al., 2013; Veriansyah et al., 2012).
2.2.1 Hydrocracking catalysts
The dual-function catalysts of hydrocracking catalysts containing two
distinctly different kinds of sites were first introduced by Mills et al. (1953) and later
expanded by Weisz et al. (1962) and Sinfeld (1983). These studies showed that both
metallic and acid sites must be present on the catalyst surface to achieve all the
desired hydroprocessing reactions, i.e. hydrogenation, dehydrogenation, hydrocracking
etc. The acidic sites promote isomerization reactions and the cracking reactions of C-C
bonds from high molecular weight hydrocarbons, while the metallic sites promote the
hydrogenation-dehydrogenation reactions. Metallic sites are the important sites since
they can avoid undesirable secondary reactions resulting in favorable hydrocracking
catalyst. Hydrogenation sites located in the proximity of the cracking (acid) sites gives
rapid molecular transfer.
2.3 Zeolite
Zeolites are inorganic porous materials. The unique structure of zeolites
pores allow some molecules to pass through their pores. Zeolite is crystalline alumino-
silicate with fully cross-linked open framework structures which contains atoms of
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silicon (aluminum) one atom and four oxygen atoms (SiO4 and AlO4) shown in Figure
2.4. Thus, zeolites are typically unique framework structures and pore diameter of 3-
13 Aº (Moissette et al., 2017).
Figure 2.5 Structure of zeolite (Marcus, Bonnie et al., 1999)
Zeolites can be classified by their chemical structure. Due to their
interesting properties such as its acidity, specific pore structure and unique shape
selectivity, they are used in various industries applications. One of the important uses
of zeolite is as catalytic crackers in processes such as hydrocracking, aromatization and
isomerization of the petrochemical industry where they are used to break the large
hydrocarbon molecules into gasoline, diesel, and kerosene (Corma, 1995; Garcia et al.,
2002; Flanigen, 1980). The advantages of zeolites are less corrosive, less toxic,
environmentally-friendly and easy modification of their acidity and pore-size by ion-
exchanging (Bin, 2007; Busca, 2007).
2.3.1 The structure of zeolite
The 3D structure of the zeolite is made up of corner sharing
aluminum oxygen tetrahedron (AlO4) and silicon oxygen tetrahedron (SiO4), consisting
of alumino-silicate at connection of the oxygen atoms which is copolymer. A
representative formula of zeolite can be presented as below:
Mn.Al2O3.xSiO2.yH2O
where n is the valence of the cation (M)
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x is the number of moles of SiO2
y is the number of moles of water in the zeolite crystals.
The classification of zeolites based on pore size and number of
tetrahedral in the ring is divided into three major groups. The first group has shape-
selective small pore size, called the 8-membered oxygen ring system. Zeolite A and
ZSM-34 are the examples of zeolites catalyst in this group. The second group is a
medium pore zeolites, known as 10-membered oxygen ring system. The unique crystal
structure like ZSM-5 zeolite are in this group.
The last group of zeolites has dual pore system, since they have
interconnecting channels between 8 – and 12 – membered oxygen ring opening or 8
– and 10 – membered oxygen ring opening. The acidic properties of catalyst in this
types can cause coke formation leading to deactivate rapidly.
(a) small pore zeolites (b) medium pore zeolites (c) large pore
zeolites
Figure 2.6 Various types of zeolites; (a) small pore zeolites, (b) medium pore zeolites,
(c) large pore zeolites (Xiaowen et al., 2006)
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2.3.2 Shape Selectivity
Three different types of the shape selectivity including reagent
selectivity, product selectivity, and transition state selectivity are shown in Figure 2.7.
Figure 2.7 Shape selectivity in zeolite channels (Csicsery et al., 1984)
Reactant shape selectivity occurs when only the certain dimensions
of the reactant molecules can permeate into zeolite pore. The reactant molecule that
has smaller diameter than the pore diameter of zeolite can enter into the pores of
zeolite and access the active sites placed in the zeolite pores. On the other hand, the
large diameter cannot diffuse into the pores of zeolite.
Product shape selectivity avoids oversized product molecules from
diffusion through the pores. However, the disadvantage of product shape selectivity is
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large molecules, which are unable to leave from the pores causing desirable product
conversion to undesired side products, coke formation and catalyst deactivation.
Transition state shape selectivity occurs when its transition state requires more space
than available space in the pores.
2.3.3 ZSM-5
ZSM-5 is a type of zeolite that comes from Zeolite Socony Mobile-
Five, was discovered in the early 60’s. ZSM-5 is constructed on 10-membered ring
building unit and these building units link together with each other to form a chain.
The interconnection of these chains then forms a channel system of the ZSM-5 as
shown in Figure 2.8.
Figure 2.8 Scheme of the channel system in ZSM-5 (Scherzer, 1990)
ZSM-5 is usually used in an acidic form. There are two types of acid
sites, which are Bronsted acid sites and Lewis acid sites. Na+ ions of the zeolites are
required to balance the framework charges by which they can be exchanged for
protons by a direct reaction with an acid giving surface Si-OH and Al-OH hydroxyl groups
and this is identified as Bronsted acid sites. If zeolite is not stable in an acid solution,
the ammonium (4NH ) salt is usually formed. After that heating is applied, a proton is
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dissociating due to the removal of ammonia. The oxygen of the hydroxyl is considered
to be three-coordinate, bridging between Si and Al. When heating is further applied,
water from the Bronsted acid sites is removed, exposing Al ion containing vacant site
of orbital which can accept electron pair, known as Lewis acid sites.
For the catalytic cracking process, the acidity of catalysts is not only
the main role in the conversion of waste virgin coconut oil but other parameters of
the microporous materials, i.e., pore size, pore volume and surface area, also influence
the % conversion and % yield of biofuel produced. The highest activity of HZSM-5 may
be attributed to its pore size which is closer to the size of triglyceride molecule. Twaiq
et al. (1999) reported the catalytic cracking palm oil over HZSM-5 and USY catalysts.
The highest yield of gaseous product over HZSM-5 is achieved.
Figure 2.9 Scheme for generating Bronsted and Lewis acid sites in zeolites (Smart and
Moore, 1992)
Many researchers have synthesized various kinds of catalysts for
catalytic cracking process. Some noble metal catalysts such as Pt, Pd, and Ru have an
excellent catalytic performance, but they are limited due to their availability and high
cost. Additionally, the noble metal catalysts are so sensitive to the catalyst
contamination that it can cause deactivation of the catalysts.
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Selection of hydrocracking catalyst for particular biofuel production
has been studied. The catalytic cracking has been studied with used palm oil as raw
material over composite zeolite (Chang and Tye, 2013). The reaction was operated
under the reaction temperature of 350˚C for an hour in a batch reactor. HZSM-5 zeolite
was selected as a catalyst in the study because of its strong acidity and shape
selectivity. To compare catalysts performance with synthesized HZSM-5 zeolite, the
zeolite catalysts were loaded with three different metals, e.g., Zn, Cu, and Mg. HZSM-
5 gave the highest yield of kerosene, while Zn-HZMS-5 catalyst gave the highest
conversion at 26.74 wt%.
The catalytic cracking of palm oil was conducted using HZSM-5 as
catalyst and the reaction was carried out between temperatures at 350°C and 500°C
for 120 min in a fixed bed reactor (Sirajudin et al., 2013). The yields of biofuels were
28.87%, gasoline, 16.20% kerosene, and 1.20% diesel. Furthermore, the HZSM-5
catalyst show more improvement in cracking palm oil to biodiesel compared to
Pt/HZSM-5 and Pd/HZSM-5 (Budianto et al., 2014). HZSM-5 catalyst impregnated by Pd
and Pt showed more enhancement for both yields of biofuels and the selectivity of
biodiesel than HZSM-5 catalyst. At a temperature of 450°C the Pt/HZSM-5 catalyst gave
the highest selectivity and yield of biodiesel of 94.6% and 67.2%, respectively. At a
temperature of 500°C the Pd/HZSM-5 catalyst gave the highest selectivity and yield of
biodiesel of 93.2% and 65.2%, respectively. At a temperature of 350°C using HZSM-5
catalyst, the highest yield of biogasoline biokerosene were 23.0% and 22.5%,
respectively while the lowest yield was 0.7% at a temperature of 400°C using Pt-HZSM-
5. The use of Pt/HZSM-5 and Pd/HZSM-5 catalysts lowered the biokerosene yield to
10.9% and 11.9%, respectively. Therefore, the Pt/HZSM-5 and Pd/HZSM-5 catalyst are
suitable for palm oil cracking process into biofuel, especially biodiesel.
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Zandonai et al. (2016) studied the production of petroleum by
hydrocracking of crude soybean oil over zeolite. The hydrocracking of soybean oil was
performed over NaZSM5 and HZSM5, which were modified ZSM5 catalyst by ion
exchange with ammonium chloride solution. The reaction was performed at 723 K and
138 kPa under a flow of hydrogen gas. The result showed that the increased acidity of
HZSM-5 improved the hydrocarbon production giving products in the range of gasoline.
After 90 min reaction time, the catalyst HZSM5 gave higher selectivity of hydrocarbon
than NaZSM5.
2.4 Parameter condition
A hydrocracking process of vegetable oils is very complex reaction system,
which is influenced by a variety of process parameters including hydrocracking
temperature, hydrogen pressure, and reaction time. In this section, some important
operating parameters are discussed.
2.4.1 Effect of temperature
Temperature, one of main parameters in hydroprocessing, influences
the biofuel yield, catalyst effectiveness and catalyst life (Scherzer and Gruia, 1996). At
the increase of temperatures, the catalyst activity increases and the catalyst
performance is deactivated faster. The removal of oxygen from the final products is
low at low temperatures, while it is more favorable at higher temperatures. The
increase of temperature is more preferable to lighter hydrocarbon production, while
the decrease of temperatures are more suitable for production of diesel range product.
As increasing temperatures, cracking reaction tends to complete resulting in an increase
of smaller and lighter molecules derived from heavy fraction product, such as
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kerosene, gasoline and gases components. Moreover, the properties of cloud point
and pour point has been improved with increasing temperature (Satyarthi et al., 2013).
In the refineries industrial, the operating over temperature range
between 553K (280°C) and 683K (410°C) are favorable. The reaction rates trend to be
slower under 553K, while the temperature above 683K favors undesirable side reaction
and coke formation on the catalyst leading to the decrease of catalyst activity
(Hobson, 1984; Speight et al., 2000). However, the reaction must be carried out at
above 350°C to eliminate the oxygenated compounds in hydrocarbon biofuel, as an
important step in formation of non-renewable fossil fuels (Muhammad et al., 2017).
Furthermore, the increase of hydrocracking temperature promotes the removal of
heteroatom (S, N and O) and deoxygenation (Bezergianni et al., 2009).
In hydrocracking of Cerbera manghas oil using Co-Ni/HZSM-5 in batch
reactor, the effect of the reaction temperature on yields of biofuel was studied by a
variation of reaction temperatures in the range between 300 and 375°C at reactor
pressure of 15 bar for 2 h (Marlinda et al., 2016). The highest yield of diesel was
obtained 46.45% at temperature of 350°C. As temperature increasing, the conversion
activity of hydrocracking of long chain of hydrocarbon molecules into short chain
hydrocarbon molecules was improved as reported in the study of Kim et al. (2013).
The effect of temperature ranging from 350 to 400°C on liquid yield
was investigated by hydrotreating of rapeseed oil with Pt/Zeolite (Pt/H-Y and Pt/HZSM-
5) and NiMo/Al2O3 catalysts in a batch reactor (Sotelo-boyas et al., 2011). At higher
temperature, the liquid yields tend to decrease, while the gas products (methane,
butane, propane and ethane) are observed. Can et al. (2013) employed the
hydrocracking of jatropha oil into green diesel by Ni-HPW/Al2O3 under various reaction
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temperatures from 300°C to 360°C. The increased temperature to 360°C gave 99.85%
conversion of jatropha oil and 85.52% selectivity of diesel fraction.
Marlinda et al. (2017) conducted the hydrocracking process at various
temperatures of 300-375°C for 2 h under hydrogen initial pressure in batch reactor
equipped with a mechanical stirrer. The yield of diesel was increased when the
temperature increasing from 300 to 350°C while the yield of diesel was reduced from
70.08% at a temperature of 350˚C to 66.42 % at a temperature of 375°C. This decline
may be attained to the occurrence of cracking of C18-C23 hydrocarbons into kerosene
(C10-C13).
The prices of the used cooking oil are cheaper than virgin vegetable
oils at least 2-3 times (Zhang et al., 2003). Bezergianni et al. (2009) studied the
hydrocracking process of used cooking oil to produce biofuel under the reactor
temperatures of 350, 370 and 390°C. As increasing the temperature to 390°C, the
conversion increased from 73% to 82%. At higher temperature, the yield of gasoline
was increased from 2 to 10%. The higher degree of cracking reaction can be achieved
with increasing temperature. As the result the feedstock molecule is converted to
diesel molecules which are further cracked into lighter molecules causing reduction of
the diesel selectivity.
The hydrotreating process of waste cooking oil under various of
reaction temperature was studied by Bezergianni et al. (2010). The process was
operated under five different reactor temperatures of 330, 350, 370, 385 and 398°C.
The results revealed that production of gasoline fraction is more favorable at higher
reactor temperatures, while that of diesel fraction are more suitable at lower reaction
temperatures.
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Table 2.3
Previous studies on the effect of temperature.
Source Catalyst Reactor Feedstock Operating parameters
Bezergianni et al. (2010) NiMo Fixed bed Waste cooking oil
T = 330-398°C
P = 80.2 bar
LSHV = 1 h-1
Sotelo-boyas et al. (2011)
Pt/H-Y
Batch Rapeseed oil
T = 300-400°C
Pt/H-ZSM-5 P = 50-110 bar
Time = 3 h
Can et al. (2013) Ni-HPW/Al2O3 Fixed bed Jatropha oil T = 300-360°C
Marlinda et al. (2016) Co-Ni/HZSM-5 Batch Cerbera manghas oil
T = 300-375°C
P = 15 bar
Time = 2 h
Marlinda et al. (2017) Co-Ni/HZSM-5 Batch Cerbera manghas oil
T = 300-375°C
P = 10-15 bar
Time = 2 h
2.4.2 Effect of hydrogen pressure
The main parameter promoting the hydrotreatment of vegetable oils
as reactants is hydrogen pressure. Operating condition at higher hydrogen pressure can
help the water removal from the catalyst to avoid excessive catalyst deactivation. The
higher hydrogen pressure favours the hydrodeoxygenation of triglycerides, while the
decarboxylation decreases (Satyarthi et al., 2013) as shown in reactions (R 2.1) and (R
2.2), respectively. Moreover, higher hydrogen feed rate favors saturation and
heteroatom removal.
Hydrodeoxygenation reaction:
CnH2n+1COOH + 3H2 Cn+1H2n+4 + 2H2O (R 2.1)
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Decarbonylation reaction:
CnH2n+1COOH CnH2n + H2O + CO (R 2.2)
Decarboxylation reaction:
CnH2n+1COOH CnH2n+2 + CO2 (R 2.3)
Kim et al. (2013) studied the effect of pressure on the liquid product
by hydroprocessed soybean oil. The experiment was operated in a batch reactor using
Ni as catalyst under a fixed operating reaction temperature of 400°C and an initial
hydrogen pressure ranging from 2.5 to 12 MPa. When increasing pressure from 9.2 to
12 MPa, the diesel yield decreased while the jet fuel selectivity increased.
At the increase of pressure, conversion and yield of diesel increase.
However, above the optimum level of operating pressure conversion increases while
diesel yield decreases. Kiatkittipong et al. (2013) conducted the hydroprocessing of
crude palm oil (CPO) using Pd/C catalyst under a variation of the hydrogen pressure
from 20 to 60 bar. The conversion of CPO progessively increased whereas diesel yield
increased to its maximum value at 40 bar and decreased at higher pressure. They
obtained the highest diesel yield of 51% under the operation of 400°C, 40 bar and
reaction time of 3 h.
Similar effects were observed in canola oil over Pt/H-Y zeolite,
Pt/HZSM-5 and NiMo/γ-Al2O3 for hydrocracking of canola oil in a batch reactor (Sotel-
Boyas et al., 2010). The experiments were carried out under three parameters including
temperature (300-400°C), initial hydrogen pressure (5-11 MPa), and hydrocracking time
(1- 6 h). The increasing initial hydrogen pressure from 8 to 10 MPa and a fixed
hydrocracking at 350°C for 3 h, diesel yield is slightly increased. The result showed that
the production of diesel fraction is affected significantly by hydrogen pressure.
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Zaher et al. (2015) studied the production of biofuel via catalytic
hydrocracking of castor oil by CoMo/Al2O3 catalyst. The experiments were carried out
under a variation of temperature between 325 and 475°C and that of hydrogen
pressure between 30 and 70 bar. The highest yield of biofuel product of 87% was
achieved at 325°C and 50 bar. Salwa et al. (2015) studied the hydrocracking of Jojoba
oil for green fuel production using zeolites as catalysts. The experiment was operated
in a high-pressure fixed bed reactor at the temperature ranging from 350 to 425°C at
the pressure of 1.0-5.0 MPa. The conversion of virgin oil to biofuel was achieved only
62.45 wt% at hydrogen pressure of 1.0 MPa. Further increasing hydrogen pressure to
5.0 MPa, conversion increased to 93.36 wt%. At higher hydrogen pressures of 5.0 MPa,
the light fractions are more predominant, therefore the high operating hydrogen
pressure is more suitable for gasoline production rather than diesel production.
To investigate the catalytic cracking of non-edible sunflower oil in a
fixed-bed reactor, ZSM-5 was used as catalyst to produce products in the range of
biojet fuel (Zhao et al., 2015). The operating reaction was operated without addition
of hydrogen at reaction temperatures of 450, 500 and 550°C. The result showed that
the highest reaction temperature at 550°C gave the highest conversion of 30.1%.
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Table 2.4
Previous studies on the effect of initial hydrogen pressure.
Reference Catalyst Reactor Feedstock Operating parameters
Sotelo-boyas et al. (2011)
Pt/H-Y
Batch rapeseed oil
T = 300-440°C
Pt/H-ZSM-5 P = 50-110 bar
Time = 3 h
Kiatkittipong et al. (2013)
Pd/C Batch palm oil T = 350-400°C P = 20-60 bar Time = 0.5-3 h
NiMo/γ-Al2O3
Kim et al. (2013) NiMo-Al2O3 Batch soybean oil T = 300-400°C P = 25-120 bar Time = 2 h
Zaher et al. (2015) CoMo-Al2O3 High pressure micro-reactor
castor oil
T = 325-475°C
P = 30-70 bar
LHSV = 1 - 4 h-1
El Khatib et al. (2015) Zeolite Fixed bed jojoba oil
T = 350-425°C
P = 10-50 bar
LHSV = 1 - 5 h-1
Zhao et al. (2015) ZSM-5 Fixed bed sunflower oil T = 450-550°C
no addition of hydrogen
2.4.3 Effect of reaction time
Increasing the residence time of reaction increases the feedstock
conversion to a certain extent. However, beyond the optimum residence time of the
hydrocracking reaction, the diesel cut products undergoes further cracking resulting in
reduction of the diesel yield.
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Rohmah et al. (2012) studied production of bio-gasoline through
catalytic hydrocracking of waste cooking oil using zeolite as catalyst. The process was
carried out in a 1.0 L autoclave and the conditions were varied temperatures (380-
420°C), initial hydrogen pressure of 8 MPa, reaction time of 60 and 90 min. The highest
yield of bio-gasoline was obtained at temperature of 400°C. The reaction time of 90
min slightly decreased the yield of bio-fuel. The longer reaction time results in
evaporation of light fraction to become gas phase.
Some researchers studied the conversion of waste cooking vegetable
oil in batch micro-reactor using sulfated zirconia as catalyst (Charusiri et al., 2006). The
experiment was operated at temperature range of 400 to 430°C, initial hydrogen
pressure between 10 and 30 bar and reaction time from 30 to 90 min. The production
of light gases and aromatics favors at the reaction time longer than 90 min.
Table 2.5
Previous studies on the effect of reaction time.
Reference Catalyst Reactor Feedstock Operating parameter
Charusiri et al. (2006)
sulfated zirconia
Batch waste cooking oil
T = 400-430°C
P = 10-30 bar
Time = 30-90 min
Rohmah et al. (2012)
Zeolite Batch waste cooking oil
T = 380-420°C
P = 8 MPa
Time = 60-90 min
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CHAPTER III
RESEARCH METHODLOGY
In this chapter, the experimental techniques and analytical methods used are
described. It is divided into three sections as the following: materials; methodology
and characterization techniques such as x-ray diffraction (XRD), scanning electron
microscopy (SEM) and temperature programmed desorption (TPD) of ammonia for
measuring surface acidity of zeolites. The reactor setup for hydrocracking process of
waste virgin coconut oil to biofuel, and the analysis of liquid products by distillation
and gas chromatography-mass spectrometry (GC-MS) technique are presented.
3.1 Chemical and reagents
Waste virgin coconut oil obtained from coconut oil extraction process
without involvement of heat. The zeolite ZSM-5, ammonium (NH4) powders were
purchased from Alfa Aesar. The mole ratio of silica (SiO2)-to-alumina (Al2O3) of the
zeolite was 80:1. Low-grade waste virgin coconut oil (Figure 3.1A) was used for batch
process while high-grade waste virgin coconut oil (Figure 3.1B) was used for continuous
process. The amount of waste virgin coconut oil from Thai Nara Company were
approximately 100-150 litre/day.
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Figure 3.1 Low-grade waste virgin coconut oil (yellow in color) (a) and High-grade
waste virgin coconut oil (clear color) (b)
Fatty acid compositions of low-grade and high-grade waste virgin coconut
oil were analyzed using Gas chromatography (Agilent Technology 7890B, Wilmington,
DE, USA) listed in Table 3.1 and Table 3.2, respectively. Waste virgin coconut oil
contains significant amount of shorter chain fatty acids. Low-grade waste virgin coconut
oil is high in lauric acid of 58 wt% while high-grade waste virgin coconut oil is high in
capric acid of 51 wt%.
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Table 3.1
Analysis data of low-grade waste virgin coconut oil
Fatty acid composition Compound Formula Retention time
(min) wt%
Caprylic acid C8H16O2 8.493 15.65
Capric acid C10H20O2 10.08 11.19
Lauric acid C12H24O2 12.275 58.79
Myristic acid C14H28O2 15.234 14.38
Table 3.2
Analysis data of high-grade waste virgin coconut oil
Fatty acid composition Compound formula Retention time
(min) wt%
Cyclohexanecarboxylic acid C7H12O2 10.60 1.30
Nonenoic acid C9H16O2 8.88 1.18
Capric acid C10H20O2 10.97 51.15
Undecylic acid C11H22O2 16.66 34.02
Dodecenoic acid C12H22O2 13.06 0.30
Lauric acid C12H24O2 21.00 12.05
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3.2 Methodology
The experimental sequence is illustrated in Figure 3.2. Each step is described in details.
Figure 3.2 Experimental procedure
START
Characterization of catalyst
Apparatus setup
Blank Test
Catalytic hydrocracking reaction condition under various Temperature (T), hydrogen pressure (P), reaction time (t)
Product separation by distillation and composition analysis by GC-MS
Preparation of catalyst
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3.2.1 Preparation of HZSM-5 zeolite
Firstly, NH4-ZSM-5 was dried at 100C for 24 hours. Then, the catalyst
NH4-ZSM-5 form zeolite was transformed to the H-form through calcination process at
550C for 5 h. The HZSM-5 catalyst was obtained (Marlinda et al., 2016; Muhammad
et al., 2017) as shown in Figure 3.3.
Figure 3.3 Scheme of HZSM-5 zeolite preparation
3.2.2 Characterization of zeolite
The characteristics of the prepared H-ZSM-5 were analyzed by the
following methods:
3.2.2.1 X-ray powder diffraction
X-ray diffraction technique is employed intensively to obtain
both qualitative and quantitative measurement on the characteristic and the
arrangement of atoms in a crystalline solid matter. X-ray diffraction (Siemens D-500,
Germany) was employed to identify and quantify of crystalline phases in the prepared
HZSM-5. The diffractometer was equipped with Cu K-α radiation 1.5418 Å at 30 mA
and 40 kV. The powder samples were scanned from 5° to 50 ° 2 at 2°/min with a
scanning step of 0.05°/step. Sample for the X-ray analysis was ground gently into a fine
powder and packed approximately 0.3-0.5 g of the sample into an aluminium sample
holder by tightening with light compression.
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3.2.2.2 Scanning electron microscopy
The scanning electron microscopy (JEOL, JSM-7800F, Japan)
was used to analyze the morphology and size distribution of the HZSM-5. Samples
were put on a thin carbon film to avoid charging effect during SEM investigation.
3.2.2.3 Temperature Programmed Desorption
Temperature programmed desorption (TPD) is used techniques
to characterize the acidity of HZSM-5. To measure the acidic and basic strength,
ammonia (NH3) was absorbed on zeolite HZSM-5. The NH3 temperature programmed
desorption (TPD) study was carried out using a heating rate of 10 ºC/min. The pulses
were continued until no more consumption of NH3 was observed.
3.2.2.4 Gas Chromatography-Mass Spectrometry (GC-MS)
The reaction reactant and product would be analyzed by GC-
MS (Gas Chromatography-Mass Spectrometry). It can analyzed both qualitatively and
quantitatively as well. The components comprised would be able to be detected by
means of the instrument with capillary column model number of Agilent Technologies
7890B, HP-Innowax for reactant (waste virgin coconut oil, WCO) and Agilent
Technologies 7890B, HP-5MS for liquid products. The condition of gas chromatography-
mass spectrometry (GC-MS) is presented in Appendix A.2.
3.3 Hydrocracking Process
The hydrocracking of waste virgin coconut oil was performed in a 200 ml
batch reactor equipped with a mechanical stirrer as shown in Figure 3.4. The operative
limits of the reactor were 200 bar and 400°C. The stirrer speed was kept constant at
350 rpm and the temperature control accuracy was ±3°C for all experiments. HZSM-5
catalyst was activated at 400°C for 4 h under a hydrogen pressure of 50 bar. For the
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hydrocracking experiment, approximately 1 g of the HZSM-5 catalyst and 100 ml waste
coconut oil was loaded in the reactor.
Leak test was conducted by loading hydrogen gas up to 70 bar at room
temperature and kept for 30 min to ensure no leak during heating and reaction.
Figure 3.4 Schematic diagram of the batch reactor
Figure 3.5 Batch reactor
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The reaction temperature for hydrocracking experiments were in a range
of 350 to 400°C and initial hydrogen pressure between 20 to 40 bar. The reaction time
was varied between 1 and 3 h to determine the optimal reaction time. The reactor
was then heated up to the final temperature by adjusting the temperature controllers.
When the conditions were reached, the reaction started. Upon the completion of the
reaction, the reactor was cooled to room temperature after finishing reaction by the
cooling unit inside of the reactor Product of hydrocracking was collected, and liquid
product was separated from catalyst by filtration. The reaction products were then
separated by distillation. Distillation technology can be used to separate an oil mixture
with wide boiling ranges into products with narrower boiling ranges. The oil mixture
was heated to vaporize the lighter components (Al-Sabawi et al., 2012). The
performance of catalysts was evaluated in terms of conversion, the yield of production
biofuel, and liquid product fraction as a follows:
𝐶𝑜𝑛𝑣𝑒𝑟𝑠𝑖𝑜𝑛 (%) = initial feedstock (g) −residue (>340˚C)after cracking
initial feedstock (g)x 100% (3.1)
𝑌𝑖𝑒𝑙𝑑(𝑤𝑡%) = weight of fractional distillation of liquid products (g)
initial feed stock (g) 𝑥 100% (3.2)
𝑆𝑒𝑙𝑒𝑐𝑡𝑖𝑣𝑖𝑡𝑦(𝑤𝑡%) = weight of target product (g)
weight of liquid product (g) 𝑥 100% (3.3)
Where initial feedstock and residue (>340C) after cracking are represented by the
wt% of the feed and product, respectively.
𝐿𝑖𝑞𝑢𝑖𝑑 𝑝𝑟𝑜𝑑𝑢𝑐𝑡 𝑓𝑟𝑎𝑐𝑡𝑖𝑜𝑛 (𝑣𝑜𝑙%) = volume of distillation fraction
total volume of distillate obtainedx 100% (3.4)
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Figure 3.6 Distillation
The yields of product were estimated from the distillation of the total
liquid product. The composition of hydrocracking liquid product was classified
according to its boiling range such as gasoline (40°C-160°C), kerosene (160°C-270°C),
and diesel (270°C-360°C). Moreover, long chain hydrocarbon molecule with boiling
point > 360°C the unconverted waste coconut oil that cannot be produced liquid
biofuels.
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CHAPTER IV
RESULT AND DISCUSSION
Results of characterization of the prepared catalyst zeolite using x-ray diffraction,
scanning electron microscopy, and temperature programmed desorption technique
were reported and discussed. The effect of operating parameters, i.e., operating
temperature, operating hydrogen pressure and reaction time, on conversion of waste
virgin coconut oil and yields of liquid biofuels was investigated to determine optimal
operating condition for biofuel production.
4.1 Characterization Analyses
4.1.1 X-ray Powder Diffraction
X-ray diffraction that used to identify multiphases pattern of HZSM-
5 is illustrated in Figure 4.1. The XRD peaks of HZSM-5 showed at the 2θ of 7-9˚ and
23-25˚. The XRD peak position and intensity of the prepared ZSM-5 catalyst are
consistent with the previously reported pattern (Zhao et al., 2015) that amorphous
impurities were not noticeably observed in the material.
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Figure 4.1 XRD patterns of HZSM-5
4.1.2 Scanning electron microscopy (SEM)
After hitting the sample with a focused beam of high-energy electron,
a detector of a scanning electron microscopy collects emitted electrons and photons,
and thus the image is obtained. The SEM images of catalysts were taken at 20000X
and 50000X magnification to observe their surface morphology in Figure 4.2 and 4.3.
The SEM pictures of H-ZSM-5 and ZSM-5 were comparable and they have shapes close
to cubic crystals.
Figure 4.2 SEM images of HZSM-5 (a) X50,000 (b) X20,000 magnificent
a b
100 nm 1 µm
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Figure 4.3 SEM images of ZSM-5 (c) X50,000 (d) X20,000 magnificent
Moreover, EDX spectrum analysis shows that the HZSM-5 structure
contained Si and Al in approximately 97.80: 2.20. (Si/Al ratio is 44.45).
Figure 4.4 EDAX Spectrum
Element Atomic %
Al 2.2
Si 97.8
Total 100
c d
100 nm 1 µm
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4.1.3 Temperature Programmed Desorption (TPD)
The NH3 desorption peaks of HZSM-5 were noticed the ranges of
temperature at 100-300 ºC (T1), 300-500 ºC (T2), 500-700 ºC (T3). The peak I may be
attributed to desorption of NH3 from weak acid sites, whereas peak II and peak III were
observed corresponding to medium and strong acid sites as summarized in Table 4.1
and the detail of TPD-NH3 is presented in Appendix A.4.
Table 4.1
Results of TPD-NH3 analysis over HZSM-5 zeolite
No. Peak type
End time
Time width
Peak position(sec)
Area(count) mmol mmol/g
1 TPx 1227 2323 1097 687,594 0.021 0.364
2 TPx 2324 3710 1387 590,231 0.018 0.312
3 TPx 3711 4807 1097 147,330 0.004 0.078
4.2 Effect of operating parameters on hydrocracking of waste virgin coconut oil
4.2.1 Effect of initial hydrogen pressure
The operating condition was evaluated at three different initial
hydrogen pressure, i.e. 20, 30, and 40 bar are shown in Table 4.2. The remaining
operating conditions were at 400˚C for 1 h over 1 g of HZSM-5.
The hydrocracking process of waste virgin coconut oil using HZSM-5
catalyst as increasing the pressure of 20 to 40 bar at a constant reaction temperature
(400°C) and reaction time (1 h), the liquid product conversion continually increased.
From Table 4.2, the highest the liquid biofuel conversion (Xl) attained was of 66.54
wt% with a hydrogen pressure of 40 bar. At initial hydrogen pressure of 20 bar, only
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63.90 wt% from the waste virgin coconut oil was transformed to liquid biofuel. Upon
increasing the pressure to 30 bar, the liquid product fractions increased to be 64.25
wt% showed in Table 4.2. The liquid product conversion (Xl) was slightly increased
with an increase in initial hydrogen pressure. It probably due to enhanced hydrogen
mass transfer on the catalyst surface, resulting in maximized use of hydrogen for
deoxygenation reactions (Srifa et al., 2015).
Table 4.2
The effect of initial hydrogen pressure on conversion (Xl), yield, and selectivity of liquid
produce fraction for waste virgin coconut oil.
Sample Yield (wt%) Selectivity (wt%) Xl
(wt%) gasoline kerosene diesel residue gasoline kerosene diesel residue
A-1 1.36 19.04 43.50 20.40 1.61 22.59 51.60 24.20 63.90
A-2 1.70 19.75 42.81 19.60 2.02 23.55 51.05 23.37 64.25
A-3 2.72 21.86 41.96 17.40 3.24 26.05 49.99 20.73 66.54
*A-1: T=400 °C, P=20 bar, t=1 h A-2: T=400 °C, P=30 bar, t=1 h A-3: T=400 °C, P=40 bar, t=1 h
When increasing in initial hydrogen pressure, the diesel yield slightly
decreased. The resulted showed the decrease in diesel yield from 43.50 wt% to 41.96
wt% as the temperature increased from 350 °C to 400 °C at a constant reaction
temperature and reaction time. However, the kerosene and gasoline yield slightly
increased with an initial hydrogen pressure. The kerosene and gasoline yield was
increased from 19.04 to 21.86 wt% and 1.36 to 2.72 wt%, respectively. The light
fractions are more predominant at initial hydrogen pressure of 40 bar, indicating that
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this technology is more suitable for kerosene production at relatively higher pressures
rather than diesel production.
The liquid produce fraction including gasoline, kerosene, and diesel
are represented in Figure 4.5. The result found that initial hydrogen pressure had
negligible effect to the overall activity in liquid produce fraction.
Figure 4.5 Effect of initial hydrogen pressure on liquid product fractions (wt%) in the
catalytic hydrocracking of waste virgin coconut oil (Conditions: Catalyst = 1 g of H-ZSM-
5, reaction temperature = 400 ˚C and time = 1 h)
By suggesting that increasing an initial hydrogen pressure from 20 to
40 bar shored insignificant effect towards the liquid product fraction. Due to when the
reaction was operated at high pressure, decarboxylation and decarbonylation as
endothermic reactions are less favoured. The hydrodeoxygenation reaction is favoured,
1.36
1.7
2.72
19.04
19.75
21.86
43.5
42.81
41.96
0 10 20 30 40 50
20 bar
30 bar
40 bar
Liquid product fraction (wt%)
Init
ial
hydro
gen
pre
ssure
(bar
)
diesel kerosene gasoline
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then result in more water forming and less liquid biofuel product because of the
deactivation of the catalyst (Kim et al., 2013).
4.2.2 Effect of reaction temperature
Reaction temperature has been the most important parameter
affecting catalyst performance. The influence of this factor on the yield and quantity
of the hydrocracked products derived from waste virgin coconut oil over HZSM-5
zeolite was studied. Three different reaction temperatures were varied i.e. 350°C,
375˚C, and 400°C while other operating conditions such as initial hydrogen pressure
and reaction period were kept constant at 40 bar for 1 h over 1 g of HZSM-5 in a
powder form. Table 4.3 shows the influence of temperature on the catalytic
hydrocracking waste virgin coconut oil.
The conversion of each reaction temperature is considered by Eq.
(3.1). Waste virgin coconut oil conversion to liquid product was found to be very much
dependent on temperature. Waste virgin coconut oil conversion decreased with
increasing temperature. When increase reaction temperature, the conversion of liquid
biofuel (Xl) decreases from 69.55 to 66.54 wt% when increase temperature from 350˚C
to 400 ˚C at a constant initial hydrogen pressure and reaction time is presented in
Table 4.3. This is because the hydrocarbons formed, cracks to gas product fraction
there by dramatically reducing the liquid product fraction.
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Table 4.3
The effect of temperature on conversion (Xl), yield, and selectivity of liquid produce
fraction for waste virgin coconut oil.
Sample Yield (wt%) Selectivity (wt%) Xl
(wt%) gasoline kerosene diesel residue gasoline kerosene diesel residue
B-1 0.35 10.58 58.62 11.80 0.43 13.00 72.06 14.51 69.55
B-2 0.57 14.11 52.45 15.60 0.69 17.05 63.40 18.86 67.13
A-3 2.72 21.86 41.96 17.40 3.24 26.05 49.99 20.73 66.54
*B-1: T=350 °C, P=40 bar, t=1 h B-2: T=375 °C, P=40 bar, t=1 h A-3: T=400 °C, P=40 bar, t=1 h
Figure 4.6 Effect of temperature on liquid product fractions (wt%) in the catalytic
hydrocracking of waste virgin coconut oil (Conditions: Catalyst = 1 g of H-ZSM-5, Initial
hydrogen pressure = 40 bar and reaction period = 1 h)
0.35
0.57
2.72
10.58
14.11
21.86
58.62
52.45
41.96
0 10 20 30 40 50 60 70
350°C
375°C
400°C
Liquid product fraction (wt%)
Tem
per
ature
(°C
)
diesel
kerosene
gasoline
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With an increasing in temperature, the diesel yield decreased from
58.62 wt% at 350 °C to 41.96 wt% at 400 °C at a constant pressure of 40 bar and the
reaction time of 1 h. Besides, diesel fraction is not favoured with temperature, while
gasoline and kerosene fractions are clearly favoured. This is expected as increasing
temperature causes more intensive cracking thus not only heavier molecules but also
some diesel molecules are further cracked into lighter molecules, there by
dramatically reducing the diesel product. Therefore at higher temperature the
hydrocracking promote gasoline and kerosene rather than diesel production.
The kerosene yield and gasoline yield increased from 10.58 to 21.86
wt% and 0.35 to 2.72 wt%, respectively as the temperature increases from 350°C to
400°C. It is consistent to the studies of that the most suitable temperature for gasoline
and kerosene production was higher than 350°C (Budianto et al., 2014; Sotelo-boyas
et al., 2008). Therefore, the reaction temperature of 350˚C is the most suitable
temperature for diesel production. Moreover, the best gasoline and kerosene fraction
of the desired liquid product can be achieved at 400˚C. On the other hand, the data
confirm the unsatisfactory results obtained for hydrocracking in case of minimizing the
reaction temperature to 350˚C.
4.2.3 Effect of reaction time
Reaction time studied in the range of 1 to 3 h. The influence of
reaction time on liquid produce fraction, under constant experimental conditions, can
be deduced from the results listed in Table 4.4. Diesel fraction is not favoured with
the time of reaction, while the increasing of reaction time is more suitable for the other
two fractions include gasoline and kerosene.
At reaction time of 60 minutes, 66.54wt% from the waste virgin
coconut oil was transformed to liquid biofuel. Upon decreasing the reaction time to
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120 minutes and 180 minutes, the liquid produce fractions was 65.64 wt% and 65.94
wt%, respectively. Increasing the time of reaction reduce the liquid product conversion
(Xl) was reduced to a certain extent as the reaction proceeds beyond the optimum
time of reaction, the diesel cut products undergoes further cracking not only to lighter
produce fraction but also gas produce fraction. Consequently, reduction of the diesel
produce fraction was observed. For waste virgin coconut oil using HZSM-5 the optimum
reaction time of produce kerosene and gasoline was found to be 180 minutes which
there is decrease in diesel produce fraction.
Table 4.4
The effect of reaction time on conversion (Xl), yield, and selectivity of liquid produce
fraction for waste virgin coconut oil.
Sample Yield (wt%) Selectivity (wt%) Xl
(wt%) gasoline kerosene diesel residue gasoline kerosene diesel residue
A-3 2.72 21.86 41.96 17.40 3.24 26.05 49.99 20.73 66.54
C-2 3.06 19.39 43.20 18.40 3.63 23.08 51.40 21.89 65.64
C-3 6.79 31.38 27.77 20.40 7.86 36.35 32.16 23.63 65.94
*A-3: T=400°C, P=40 bar, t=1 h C-2: T=400°C, P=40 bar, t=2 h C-3: T=400°C, P=40 bar, t=3 h
As it is evident from Figure 4.7, the light fractions are more
predominant at reaction time of 180minutes, indicating that long time of reaction is
more suitable for gasoline and kerosene fraction than diesel produce fraction until
overcracking.
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Figure 4.7 Effect of reaction time on liquid product fractions (wt%) in the catalytic
hydrocracking of waste virgin coconut oil (Conditions: Catalyst = 1 g of H-ZSM-5,
Pressure = 40 bar and temperature = 400˚C)
As increasing in the reaction time, the diesel yield dramatically
decreased. The diesel yield decreased from 41.96 wt% at 1 h to 27.77 wt% at 3 h at a
constant reaction temperature and initial hydrogen pressure. However, the kerosene
and gasoline yield increased with the reaction time. The kerosene and gasoline yield
was increased from 21.86 to 31.38 wt% and 2.72 to 6.79 wt%, respectively.
Therefore, the reaction time of 120 minutes is the most suitable
temperature for diesel production. Moreover, it could be regarded as the most suitable
temperature for the light fraction product, particularly kerosene, can be realized the
reaction time of 180 minutes. For the longer time of reaction, the liquid biofuel
undergoes further cracking to the lighter produce fraction and reduces the diesel
produce fraction.
2.72
3.06
6.79
21.86
19.39
31.38
41.96
43.2
27.77
0 20 40 60 80
60 min
120 min
180 min
Liquid product fraction (wt%)
Rea
ctio
n t
ime
(min
)diesel
kerosene
gasoline
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4.3 Data analysis from the input-output model
A quantitative predictive linear model based on can be determined by
calculating input-output coefficients of values of input (reaction temperature, initial
hydrogen pressure, and reaction period) and output (yields of gasoline, kerosene and
diesel). The set of experimental data of hydrocracking of waste virgin coconut oil for
producing liquid biofuel was modeled to estimate input-output coefficients as follows:
The input-output model was proposed as Z = + P + T +t (4.1)
Where Z = 7x1 vector of liquid biofuel yields {YX/S} under all seven conditions,
P = pressure, {20, 30, 40} bar,
T = temperature, {350, 375, 400} ºC,
t = reaction time, {1, 2, 3} h.
It can be written in matrix form as follows:
Z = AB or B = A-1Z
Where A = 74 matrix of the total experimental conditions,
B = 41 vector of model coefficients, [ ]T.
𝑍 = 𝑌𝑔𝑎𝑠𝑜𝑙𝑖𝑛𝑒 = 1 + 1
𝑃 + 1
𝑇 + 1𝑡 (4.2)
𝑍 = 𝑌𝑘𝑒𝑟𝑜𝑠𝑒𝑛𝑒 = 2 + 2𝑃 +
2𝑇 + 2𝑡 (4.3)
𝑍 = 𝑌𝑑𝑖𝑒𝑠𝑒𝑙 = 3 + 3
𝑃 + 3
𝑇 + 3𝑡 (4.4)
The model coefficients were determined by solving a linear matrix
equation with Matlab (Mathworks, MA, USA) as shown in Table 4.5
.
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Table 4.5
The calculated correlation coefficients
α β γ δ
α1 -16.216 β1 0.0298 γ1 0.0371 δ1 2.146 α2 -58.542 β2 0.0044 γ2 0.1822 δ2 4.82 α3 163.229 β3 0.08 γ3 -0.287 δ3 -7.0143
The proposed input-output models were as follows:
Ygasoline = -16.2160 + 0.0298P + 0.0371T + 2.1460t (4.5)
Ykerosene = -58.5420 + 0.0044P + 0.1822T + 4.8200t (4.6)
Ydiesel = 163.2290 + 0.0800P - 0.2870T– 7.0143t (4.7)
Eqs. (4.5)-(4.7) were plotted as shown in Figures 4.8-4.10.
A positive value of represents favorable effect on Ydiesel while a negative
value of represents unfavorable effect on Ykerosene and Ygasoline. The increase of
reaction temperature and reaction time had insignificantly adverse effect on Ydiesel as
shown in corresponding Figures 4.8 and 4.10. Moreover, the increase of reaction time
and temperature had positive effect on Ygasoline and Ykerosene as shown in Figures 4.8 and
4.10. The increase of initial hydrogen pressure had no significant effect on Ykerosene,
Ygasoline, and Ydiesel.
Ref. code: 25605810030592YLH
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Figure 4.8 The input-output correlation of the effect of initial hydrogen pressure (P)
Figure 4.9 The input-output correlation of the effect of reaction temperature (T).
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Figure 4.10 The input-output correlation of the effect of reaction time (t).
4.4 Accuracy of models used in liquid biofuel yield prediction
The coefficient of determination that gave a good fit as estimated R2 values
of yield prediction models of gasoline, kerosene, and diesel was 0.9227, 0.8605, and
0.9133, respectively as shown in Figures 4.11-4.13. This shows better fit between
modeled and observed data of Ygasoline and Ydiesel than that of Ykerosene.
Figure 4.11 Correlation between actual and predicted yield for gasoline
y = 0.9231x + 0.1759
R² = 0.9227
0.0
1.0
2.0
3.0
4.0
5.0
6.0
7.0
0.0 2.0 4.0 6.0 8.0
Pre
dic
ted
Yie
ld
Actual Yield
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Figure 4.12 Correlation between actual and predicted yield for kerosene
Figure 4.13 Correlation between actual and predicted yield for diesel
4.5 Data analysis – Pearson’s correlation coefficient
Pearson’s correlation coefficient is a statistical measure of association
strength between two variables. Pearson’s correlation ranges between +1 and -1 where
+1 shows a perfect relationship, -1 shows adverse relationship and 0 indicates no
associaton between two variables. An r value indicates strength in relationship
y = 0.8601x + 2.7051
R² = 0.8605
0.0
5.0
10.0
15.0
20.0
25.0
30.0
35.0
0.0 10.0 20.0 30.0 40.0
Pre
dic
ted Y
ield
Actual Yield
y = 0.913x + 3.8651
R² = 0.9133
0.0
10.0
20.0
30.0
40.0
50.0
60.0
70.0
0.0 20.0 40.0 60.0 80.0
Pre
dic
ted Y
ield
Actual Yield
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between variables as follows: 0 r 0.29, weak; 0.30 r 0.39, moderate; 0.40
r 0.69, strong; and r 0.70, very strong.
For the yield of data, SPSS (version 16, chicago, IL, U.S.) produces the following
correlation output:
Table 4.6
Pearson’s correlation coefficients of yields of liquid biofuel with reaction temperature
(T), initial hydrogen pressure (P), and reaction time (t).
*Significant level or p-value of 0.05
**Significant level or p-value of 0.01
The yield of diesel (Ydiesel) and that of kerosene (Ykerosene) have no
relationship with initial hydrogen pressure (P) indicating P dependence is negligible as
shown in Table 4.6. Moreover, the Ygasoline has a weak positive relationship with P
indicating P dependence of the Ygasoline. Hydrogen pressure is necessary to avoid
deactivation of the catalyst (Donnis et al., 2009; Maki-Arvela et al., 2007). Higher
pressure would enhance the absorbed hydrogen on the surface active sites promoting
hydrodeoxygenation and it produces more water, which may deactivate the catalyst.
Pearson's correlation T P T
Ygasoline Correlation coefficient (r) 0.561 0.258 0.921**
Sig. (2-tailed) 0.190 0.576 0.003
Ykerosene Correlation coefficient (r) 0.749 0.016 0.773*
Sig. (2-tailed) 0.053 0.972 0.042
Ydiesel Correlation coefficient (r) -0.809 0.070 -0.755
Sig. (2-tailed) 0.028 0.882 0.050
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When increasing the initial hydrogen pressure, the improvement of Ygasoline was slightly
more noticeable than that of Ykerosene and Ydiesel. It was consisitent with the study of
Sotelo-boyas et al. (2011) that the Ydiesel is not affected significantly by the pressure.
The Pearson’s correlation coefficients in Table 4.6 shows very strong
negative relationship of the Ydiesel with reaction temperature (T) and time (t) with
corresponding r values of -0.809 and -0.755. On the other hand, the Ykerosene shows very
strong positive relationship with T and t with corresponding r values of 0.749 and 0.773.
The Ygasoline shows very strong positive relationship with t with r value of 0.921 while
this shows strong positive relationship with T with r value of and 0.561. It indicated
that the temperature mainly affected the thermal cracking of long chain hydrocarbon
into light products, and further cracking resulting in a light hydrocarbon gaseous
product with increasing the reaction time. At higher temperature and longer
hydrocracking reaction time, hydrodeoxygenation was favored while the yield of liquid
products was directly affected (Budianto et al., 2014). As shown in Table 4.6, the Ydiesel
was dramatically decreased with increase of temperature, probably due to the
continued cracking reaction of the long chain hydrocarbons to light products such as
kerosene and gasoline. At temperatures above 350C, the capacity of cracking of n-
paraffins and iso-paraffins in the boiling range of diesel was enhanced; which in turn,
the yield of light product fractions as gasoline and kerosene was increased.
4.6 The Reaction Product Distribution
4.6.1 The number of carbon atom
The product samples were collected and analyzed by gas
chromatography (GC-MS). The composition of hydrocracking liquid product was
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classified according to the number of carbon atom such as gasoline (< C8), kerosene
(C9-C12), diesel (C13-C18), and heavy fraction (> C18). The product distribution of C7-C26
hydrocarbons under the various reaction conditions over HZSM-5 catalysts presents as
Figures 4.14 -4.1 6 . Increasing hydrogen pressure increased water removal from the
catalyst to avoid excessive catalyst deactivation. The initial hydrogen pressure as
studied in the range of 20 to 40 bar. The highest distribution of hydrocarbons was in
the range of C11.
Figure 4.14 The effect of initial hydrogen pressure on the distribution of carbon atom
number of liquid products yielded from hydrocracking process over HZSM-5
The increase of temperature was more preferable to lighter
hydrocarbon production, while the decrease of temperatures was more suitable for
production of diesel range product (C13-C18). At the lowest reaction temperature of
350°C, the main product was in the range of C13 as shown in Figure 4.15. Higher
temperature leads to more complete cracking reaction resulting in the increase of
smaller and lighter molecules derived from heavy fraction products, such as kerosene
and gasoline. The elevated reaction temperature improves the catalyst activity;
0
5
10
15
20
25
30
35
40
C7 C8 C9 C10 C11 C12 C13 C14 C15 C16 C17 C18 C19 C20 C21 C22 C23 C24 C25 C26
Sel
ecti
vit
y (
%)
The number of carbon atom
20 bar
30 bar
40 bar
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however, the catalyst performance tends to be deactivated faster (Gutierrez et al.,
2012).
Longer time of reaction brings more conversion of waste virgin
coconut oil to the heavy cracked fraction which was further cracked to the lighter
product fraction. At the reaction time of 120 minutes, the distribution of hydrocarbons
were in the range of C7 (gasoline) and C13-C18 (diesel). When the reaction time was
increased to 180 minutes, the highest distribution of hydrocarbons were in the range
of C9-C11 defined as kerosene range as shown in Figure 4.16.
Figure 4.15 The effect of reaction temperature on the distribution of carbon atom
number of liquid products yielded from hydrocracking process over HZSM-5
0
5
10
15
20
25
30
35
40
45
C7 C8 C9 C10 C11 C12 C13 C14 C15 C16 C17 C18 C19 C20 C21 C22 C23 C24 C25 C26
Sel
ecti
vit
y (
%)
The number of carbon atom
350 C
375 C
400 C
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Figure 4.16 The effect of reaction time on the distribution of carbon atom number of
liquid products yielded from hydrocracking process over HZSM-5
4.6.2 Selectivity of kerosene range hydrocarbon
The product distribution of kerosene range over the HZSM-5 catalyst
was shown in Figures 4.19-4.20 and the number of hydrocarbon C9 - C12 are the main
component in jet fuel. There are many types of compounds in kerosene fraction,
including alkanes, alkenes, and aromatics. The product selectivity in kerosenerange
hydrocarbons containing a C = C double bond known as alkenes which were the major
kerosene fraction under the various conditions.
0
5
10
15
20
25
30
35
40
C7 C8 C9 C10 C11 C12 C13 C14 C15 C16 C17 C18 C19 C20 C21 C22 C23 C24 C25 C26
Sel
ecti
vit
y (
%)
The number of carbon atom
60 minutes
120 minutes
180 minutes
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Figure 4.17 The effect of reaction temperature on the selectivity for kerosene fraction
towards formation of aromatic, alkane, and alkene
Figure 4.18 The effect of initial hydrogen pressure on the selectivity for kerosene
fraction towards formation of aromatic, alkane, and alkene
aromatic
alkane
alkene
0
20
40
60
80
100
350 375 400
Sel
ecti
vit
y o
f ker
ose
ne
ran
ge
hyd
roca
rbo
ns
(%)
Reaction temperature (°C)
aromatic
alkane
alkene
0
20
40
60
80
100
20 30 40
Sel
ecti
vit
y o
f ker
ose
ne
range
hydro
carb
ons
(%)
Initial hydrogen pressure (bar)
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Figure 4.19 The effect of reaction time on the selectivity for kerosene fraction
towards formation of aromatic, alkane, and alkene
4.7 Degree of deoxygenation (DOD) and degree of cracking (DOC)
4.7 .1 Effect of reaction parameters on the degree of deoxygenation
(DOD) and degree of cracking (DOC) in the batch reactor
To analyze the degree of deoxygenation (DOD) of organic acids in the
oil is calculated using Eq. (4.8) correlating the organic oxygenated compounds
produced (Ox). For evaluating the cracking extent of reaction, the degree of cracking
(DOC), Eq. (4.9), was used, which is the relation of the amount of carboxylic acids in
products and in feed. Eqs. (4.8) and (4.9) are expressed as follows:
𝐷𝑒𝑔𝑟𝑒𝑒 𝑜𝑓 𝑑𝑒𝑜𝑥𝑦𝑔𝑒𝑛𝑎𝑡𝑖𝑜𝑛 = (1 −𝑂𝑥𝑦𝑔𝑒𝑛𝑎𝑡𝑒𝑑𝑝𝑟𝑜𝑑𝑢𝑐𝑡
𝑂𝑥𝑦𝑔𝑒𝑛𝑎𝑡𝑒𝑑𝑓𝑒𝑒𝑑) ∗ 100 (4.8)
𝐷𝑒𝑔𝑟𝑒𝑒 𝑜𝑓 𝑐𝑟𝑎𝑐𝑘𝑖𝑛𝑔 = (1 −𝑐𝑎𝑟𝑏𝑜𝑥𝑦𝑙𝑖𝑐 𝑎𝑐𝑖𝑑𝑝𝑟𝑜𝑑𝑢𝑐𝑡
𝑐𝑎𝑟𝑏𝑜𝑥𝑦𝑙𝑖𝑐 𝑎𝑐𝑖𝑑𝑓𝑒𝑒𝑑) ∗ 100 (4.9)
aromatic
alkane
alkene
0
20
40
60
80
100
60 120 180
Sel
ecti
vit
y o
f ker
ose
ne
ran
ge
hyd
roca
rbo
ns
(%)
Reaction time (min)
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Temperature is an operating parameter affecting hydrocracking
catalysts activity which is evaluated by the degree of deoxygenation and degree of
cracking expressed in corresponding Eqs. (4.8) and (4.9). The degree of cracking (DOC)
and degree of deoxygenation (DOD) of waste virgin coconut oil for the HZSM5 at the
reaction temperature range of 350°C and 400°C are presented in Figures 4.20 and 4.21,
respectively. As increasing the reaction temperature from 350°C to 400°C, the DOD was
increased to 11.99 % or by a factor of 1.31 (Figure 4.20) and the DOC was increased to
13.59 % or by a factor of 1.62 (Figure 4.21 ). This was attained that the amount of
triglyceride are more cracked to light products by increasing reaction temperature
(Gutierrez et al., 2012).
Figure 4.20 The Effect of the reaction temperature on the degree of deoxygenation
over HZSM-5 catalysts
5.18
8.13
11.99
0
5
10
15
20
340 350 360 370 380 390 400 410
Deg
ree
of
Deo
xygen
atio
n [
DO
D]
Reaction temperatre [°C]
Ref. code: 25605810030592YLH
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Figure 4.21 The effect of the reaction temperature on the degree of cracking on over
HZSM-5 catalysts
Since the presence of hydrogen is insufficient to avoid coke
formation resulting in deactivation of the catalysts, it is needed to split off the fatty
acids from the glycerides for the further reactions (Xu et. al., 2010). In Figures 4.22 and
4.23, the effects of initial hydrogen pressure ranging from 20 to 40 bar on the DOC and
the DOD of waste virgin coconut oil for the HZSM-5 catalysts are presented. The result
showed that initial hydrogen pressure had negligible effect on the degree of
deoxygenation and degree of cracking.
5.18
8.75
13.59
0
5
10
15
20
340 350 360 370 380 390 400 410
Deg
ree
of
crac
kin
g [
DO
C]
Reaction temperature [°C]
Ref. code: 25605810030592YLH
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Figure 4.22 The effect of the initial hydrogen pressure on the degree of
deoxygenation on over HZSM-5 catalysts
Figure 4.23 The effect of the initial hydrogen pressure on the degree of cracking on
the over HZSM-5 catalysts
11.20 11.5911.99
0
5
10
15
20
15 20 25 30 35 40 45
Deg
ree
of
Deo
xygen
atio
n [
DO
D]
Initial hydrogen pressure [bar]
12.50 12.6413.59
0
5
10
15
20
15 20 25 30 35 40 45
Deg
ree
of
crac
kin
g [
DO
C]
Initial hydrogen pressure [bar]
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In general, as the reaction proceeds, the content of liquid
hydrocarbon in products increases, following by drastic increase of the DOC to 33.58
% as shown in Figure 4.24 . The DOD also was increased to 31.16 % as the reaction
time increased (Figure 4.25 resulting in formation of non-deoxygenated liquid product.
Figure 4.24 The effect of the reaction time on the degree of deoxygenation over
HZSM-5 catalysts
Figure 4.25 The effect of the reaction time on the degree of cracking over HZSM-5
catalysts
11.9910.06
31.16
0
5
10
15
20
25
30
35
40 60 80 100 120 140 160 180 200
Deg
ree
of
deo
xygen
atio
n [
DO
D]
Reaction time [min]
13.5912.16
33.58
0
5
10
15
20
25
30
35
40 90 140 190
Deg
reee
of
crac
kin
g [
DO
C]
Reaction time [min]
Ref. code: 25605810030592YLH
64
4.8 Continuous process
4.8.1 Experimental
The continuous hydrocracking lab-scale process of waste virgin
coconut oil was performed in a fixed bed reactor as shown in Figure 4. 26 . A 0.1 gram
of HZSM-5 catalyst was packed in the fixed bed reactor column and the hydrocracking
temperature cannot be exceeded the upper temperature limit of 350°C. The effect of
hydrogen flow rate was varied between 20 ml/min and 50 ml/min at the feedstock
flow rate of 0.06 ml/min. The fixed bed column length and fixed-bed column diameter
were 10 cm and 0.18 inch (0.4572 cm), respectively. The amount of waste virgin
coconut oil was flowed together with hydrogen in to the laboratory-scale continuous
reactor packed with the prepared HZSM-5 catalyst.
Figure 4.26 Reactor set-up
4.8.2 Product Analysis
The reactions were conducted for 30 to 90 mins. The products were
collected and analyzed by using GC/MS (Model: 7890B, Agilent Technologies, USA). In
this study, the gas product and coke yield were undetermined. The decanoic acid (DA)
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65
as a rich feed. The calculation of conversion was based on the amount of decanoic
acid (C10H20O2) in feed and in product as expressed in Eq. (4.10).
𝐶𝑜𝑛𝑣𝑒𝑟𝑠𝑖𝑜𝑛 (%) = 𝑑𝑒𝑐𝑎𝑛𝑜𝑖𝑐 𝑎𝑐𝑖𝑑𝑓𝑒𝑒𝑑−𝑑𝑒𝑐𝑎𝑛𝑜𝑖𝑐 𝑎𝑐𝑖𝑑𝑝𝑟𝑜𝑑𝑢𝑐𝑡
𝑑𝑒𝑐𝑎𝑛𝑜𝑖𝑐 𝑎𝑐𝑖𝑑𝑓𝑒𝑒𝑑 𝑥 100 (4.10)
At a variation of hydrocracking hydrogen feed rate, decanoic acid
conversion was examined and reported in Figure 4.27. The conversion of decanoic acid
was between 91 to 99 % with the various the hydrogen flow rate range of 20 to 50
ml/min.
Figure 4.27 Decanoic acid conversion over HZSM-5 as function of time
4.8.3 Effect of hydrogen flow rate
Hydrogen flow rate which serves as the reactant is also used as a
carrier gas. Hydrogen flow rate is inversely proportional to the residence time of
reactant molecules on the surface of the catalyst. Thus, the higher the flow rate, the
shorter the residence time of reactant molecules on the surface of the catalyst.
0
20
40
60
80
100
30 60 90
Conver
sion (
%)
reaction time (minutes)
20 ml/min
30 ml/min
40 ml/min
50 ml/min
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The hydrogen flow rate ranging from 20 to 50 ml/min significantly
affected the yield of bio-kerosene fraction at the reaction time of 30 mins as shown in
Figure 4.28. The fraction of bio-kerosene produced from the HZSM-5 catalyzed cracking
reaction of waste virgin coconut oil has the opposite trend to the formation of the bio-
gasoline fraction. The produced bio-kerosene fraction increased from 0.40% to 9.04%
with increasing flow rate up to 40 ml/min. Further increase of the hydrogen gas flow
rate to 50 mL/min, the amount of bio-kerosene fraction decreased. This may be
attributed that the hydrogen flow rate higher than 40 ml/min enhanced secondary
cracking and lighter product formation.
Figure 4.28 The effect of the hydrogen flow rate on product formation at the reaction
time 30 minutes
The result shows no significant changes in bio-gasoline fraction
product when increasing the reaction time to 60 minutes and increasing the hydrogen
flow rate as shown in Figure 4.29, the highest bio-kerosene was 15.27% at the hydrogen
0.57
0.00 0.00
5.00
0.40
4.81
9.04
0.47
3.58
0.00 0.00
2.71
0
1
2
3
4
5
6
7
8
9
10
0 10 20 30 40 50 60
Yie
ld [
%]
Hydrogen flow rate [ml/min]
Reaction time 30 min gasoline
kerosene
>C13
Ref. code: 25605810030592YLH
67
flow rate of 50 ml/min. Thus, the hydrogen flow rate of 50 ml/min and the reaction
time of 60 minutes are the most appropriate condition for formation of bio-kerosene
range product.
The effect of the hydrogen flow rate ranging from 20 to 50 ml/min
was studied by increasing the reaction time up to 90 minutes as shown in Figure 4.30.
The formation of products in the range of bio-gasoline and bio-kerosene was not
observed, although the hydrogen flow rate increased. This may be attributed that
longer reaction time causes the catalyst deactivated at the longer reaction time.
Figure 4.29 The effect of the hydrogen flow rate on product formation at the reaction
time 60 minutes
0.000.00
0.00 0.00
11.40
0.052.39
20.68
14.41
6.90
0.00
5.29
0
5
10
15
20
25
0 10 20 30 40 50 60
Yie
ld (
wt%
)
Hydrogen flow rate [ml/min]
Reaction time 60 mingasoline
kerosene
>C13
Ref. code: 25605810030592YLH
68
Figure 4.30 The effect of the hydrogen flow rate on product formation at the reaction
time 90 minutes
4.8.4 Effect of reaction time on catalyst activity and selectivity to
product
Cracking reactions with variation of reaction time were performed at
a hydrogen flow rate of 50 ml/min since this flow rate was capable of producing the
highest fraction of kerosene. The fraction of bio-kerosene was increased from 0.43 %
to 20.68 % with increasing the reaction time up to 60 minutes. After 60 minutes of
reaction time, the kerosene fraction significantly decreased to 0.80 %. Furthermore at
the increase of the reaction time, the gasoline fraction decreased while the heavy
fraction (>C13) increased. The prolonged reaction time probably caused a decrease in
catalyst activity due to coke deposition covering the active site of the catalyst.
0.27
0.00 0.000.00
2.42
1.430.68 0.80
17.41
0.67
0.00
4.13
0
2
4
6
8
10
12
14
16
18
20
0 10 20 30 40 50 60
Yie
ld (
wt%
)
Hydrogen flow rate [ml/min]
Reaction time 90 min
gasoline
kerosene
>C13
Ref. code: 25605810030592YLH
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Figure 4.31 The effect of a reaction time with the hydrogen flow rate 50 ml/min
The effect of hydrogen flow rate on the selectivity to product at a
variation of the reaction time was shown Figures 4.32 -4.34 . A biofuel selectivity is
defined in Eq. (4.10)
𝑆𝑒𝑙𝑒𝑐𝑡𝑖𝑣𝑖𝑡𝑦(𝐶𝑥𝐻𝑦) (%) = (𝐶𝐻)𝑛𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠
∑(𝐶𝐻)𝑛𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 𝑥 100 (4.10)
With increasing the hydrogen flow rate from 20 to 50 ml/min at the
reaction time 30 minutes, the gasoline selectivity reached 58.60 % and then decreased
sharply at the reaction time 60. As increasing the reaction time to 60 and 120 minutes,
the main product components were in the range of kerosene.
5.00
0.000.00
0.47
20.68
0.80
2.71
5.294.13
0
5
10
15
20
25
0 20 40 60 80 100
Yie
ld (
wt%
)
Progress of reaction[min]
gasoline
kerosene
>C13
Ref. code: 25605810030592YLH
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Figure 4.32 The effect of hydrogen flow rate on the selectivity to product at 30
minutes
Figure 4.33 The effect of hydrogen flow rate on the selectivity to product at 60
minutes
gasoline
kerosene
diesel
0
20
40
60
80
100
20 30 40 50
Sel
ecti
vit
y (
wt%
)
Hydrogen flow rate (ml/min)
reaction time 30 minutes
gasoline
kerosene
diesel
0
20
40
60
80
100
20 30 40 50
Sel
ecti
vit
y (
wt%
)
Hydrogen flow rate (ml/min)
reaction time 60 minutes
Ref. code: 25605810030592YLH
71
Figure 4.34 The effect of hydrogen flow rate on the selectivity to product at 120
minutes
gasoline
kerosene
diesel
0
20
40
60
80
100
20 30 40 50
Sel
ecti
vit
y (
wt%
)
Hydrogen flow rate (ml/min)
reaction time 120 minutes
Ref. code: 25605810030592YLH
72
CHAPTER V
CONCLUSION AND RECOMMENDATIONS
5.1 Conclusion
The performance of zeolite (HZSM-5) catalysts was prepared for the
hydrocracking of waste virgin coconut oil to produce gasoline, kerosene (Jet fuel) and
diesel range in a laboratory-scale batch reactor. The operating parameters were a
temperature range of 350 to 400ºC, operating pressure range of 20 to 40 bar and
reaction time range of 1 to 3 h.
Our findings can be concluded as the followings.
1.The increase of the reaction temperature favoured hydrocracking process to
light hydrocarbon products such as kerosene and gasoline while it did not favor
hydrocracking process to heavy hydrocarbon product such as diesel. Pressure
dependence on yields of biofuels derived from hydrocracking of waste virgin coconut
oil was insignificant.
2. Longer time favoured hydrocracking process to lighter fraction products such
as gasoline and kerosene. On the conversely, diesel production was not favoured by
longer time operation.
3. Based on the experiments, the highest yield of gasoline and kerosene was
obtained when the operated condition were 400°C, 40 bar, and 3 h and the operated
condition at 350°C, 40 bar, and 1 h gave the highest yield of diesel.
4. Strength relationships among the three operating parameters using the
Pearson’s correlation coefficients showed strong dependence of reaction temperature
and time on Ygasoline and Ykerosene, but strong adverse relationship with Ydiesel.
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73
5.2 Recommendations
The recommendations for further study are listed as follows:
1. Initial hydrogen pressure was responsible for the steps of catalytic cracking
and hydrogenation. Based on the experiments, the effect of initial hydrogen pressure
has been studied in the range between 20 and 40 bar and the result found that the
initial hydrogen pressure has not only weakly affected but also no significant effect
observed on the yields of biofuel. It is recommended that hydrogen pressure higher
than 40 bar should be studied in further work.
2. The result suggests that hydrocracking reactions are favoured at higher
temperatures since the liquid products are breaking down to form more gas products.
In this work the highest operating temperature was 400°C that improved the yield of
kerosene and gasoline. It is recommended that the temperature range between 400-
500°C for biofuel production should be studied in further work.
3. A comprehensive kinetic model and reaction mechanisms for hydrocracking
process of waste virgin coconut oil should be developed for large-scale production
and optimization of hydrocracking process.
Chemical Reaction Model
The applied rates of reactions in hydrocracking process are expressed as follows:
−𝑟𝑓𝑒𝑒𝑑 = 𝐾𝐶𝑓𝑒𝑒𝑑
where K and 𝐶𝑓𝑒𝑒𝑑 are reaction rate constant and feed concentration, respectively.
The reaction constant can be estimated by Arrhenius equation as follows:
𝐾 = 𝐴𝑒𝑥𝑝(−𝐸𝑎
𝑅𝑇)
Ref. code: 25605810030592YLH
74
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APPENDICES
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APPENDIX A
RAW DATA OF CHARACTERIZATION
APPENDIX A.1: Raw data of gas chromatography-mass spectrometry
Table A.1
Compositional analysis of low-grade waste virgin coconut oil
Fatty acid composition Compound
Formula Retention time
(min) wt%
C8:0 Caprylic acid C8H16O2 8.493 15.65
C10:0 Capric acid C10H20O2 10.08 11.19
C12:0 Lauric acid C12H24O2 12.275 58.79
C14:0 Myristic acid C14H28O2 15.234 14.38
Table A.2
Compositional analysis of high-grade waste virgin coconut oil
Fatty acid composition Compound
formula
Retention time
(min) wt%
Cyclohexanecarboxylic acid C7H12O2 10.60 1.30
Nonenoic acid C9H16O2 8.88 1.18
Capric acid C10H20O2 10.97 51.15
Undecylic acid C11H22O2 16.66 34.02
Dodecenoic acid C12H22O2 13.06 0.30
Lauric acid C12H24O2 21.00 12.05
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APPENDIX A.2: Condition of Gas Chromatography-Mass Spectrometry
APPENDIX A.2.1: Condition of Gas Chromatography-Mass Spectrometry (GC-MS) for
reactant (high-grade waste virgin coconut oil)
GC
Model Agilent Technologies 7890B
Mode of Injection
Liquid/Split 20:1
Injection volumn
2.0 µL
Injection temperature
250°C
GC Column HP-Innowax
GC Oven Rate(°C/min) Value (°C) Hold time
(min) Run time (min)
50 1 1
25 200 0 7
3 230 23 40
MS
Model
Agilent
Techologies
5977A
Ion Source EI
Source Temp. 230 °C
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APPENDIX A.2.2: Condition of Gas Chromatography-Mass Spectrometry (GC-MS) for
liquid products (Batch process)
GC
Model
Agilent
Technologie
s 7890B
Mode of
Injection
Liquid/Split
50:1
Injection
volumn 0.5 µL
Injection
temperature 220°C
GC Column HP-5MS
GC Oven Rate(°C/min) Value (°C) Hold time
(min) Run time (min)
35 10 10
10 200 10 36.5
Quad Temp. 150 °C
Fixed Electron E. 70 eV
Acquisition Type Scan
Start Mass (m/z) 46 End Mass
(m/z) 500
Frequency
(scans/sec) 4.4
Solvent Cut
Time (min) 1.6
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MS
Model
Agilent
Techologies
5977A
Ion Source EI
Source Temp. 230 °C
Quad Temp. 150 °C
Fixed Electron
E. 70 eV
Acquisition
Type Scan
Start Mass
(m/z) 10
End Mass
(m/z) 600
Frequency
(scans/sec) 2.5
Solvent Cut
Time (min) 3.6
APPENDIX A.2.3: Condition of Gas Chromatography-Mass Spectrometry (GC-MS) for
liquid products (Continuous process)
GC
Model
Agilent
Technologies
7890B
Mode of Injection Liquid/Split
20:1
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Injection volumn 0.5 µL
Injection
temperature 250°C
GC Column HP-5MS
GC Oven Rate(°C/min) Value (°C) Hold time (Min) Run time (Min)
35 10 10
10 300 5 30
MS
Model Pegasus 4D-
C, Leco,USA
Ion Source EI
Source Temp. 300°C
Quad Temp. 230°C
Fixed Electron E. 70 eV
Acquisition Type Scan
Start Mass (m/z) 46 End Mass
(m/z) 500
Frequency
(scans/sec) 4.4
Solvent
Cut Time
(min)
4
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APPENDIX A.3: XRD Analysis
Table A.3
Data of Theta and six highest peaks of zeolite and H-zeolite
Catalyst Theta FWHM (deg) Particle size (nm) Average particle
size (nm)
HZSM-5 7.924 0.148 56.24 18.34
8.315 4.089 2.04
22.675 0.442 19.46
23.127 1.168 7.26
23.154 0.394 21.51
24.409 2.221 3.83
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APPENDIX A.4: Temperature programmed desorption of ammonia
Table A.4
Raw data of temperature programmed desorption of ammonia
Pretreatment Parameters
Number of pretreatment step 6
Sample weight 0.0569 g
STEP Gas name Flow rate (ml/min) Time (min) Target temperature (ºC)
1 He 50 50 500
2 He 50 60 500
3 He 50 1 100
4 He 50 10 100
5 NH3/He 50 30 100
6 He 50 15 100
Measurement Condition
Time for detector stabilization 20
Target temperature 610
Ramp rate 10
Target temperature holding time 20
Carrier gas name He
Flow 1 30
Flow 2 0
Number of Mix line 0
MFC Total flow 30
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Figure A.1 NH3-TPD of HZSM-5
APPENDIX A.5: Test method: ASTM D 3278-96(R11) (Flash point Analysis)
Table A.5
Flash point Analysis
Initial hydrogen pressure (bar) 20 30 40
Kerosene Flash point (deg. C)
60 75 54
Diesel 120 120 99
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APPENDIX B
RAW DATA OF EXPERIMENTSL RESULTS
Table B.1
Experimental conditions
Sample Reaction temperature
(˚C) Initial pressure (bar) Reaction time (h)
A-1 400 20 1
A-2 400 30 1
A-3 400 40 1
B-1 350 40 1
B-2 375 40 1
B-3 or A-
3 400 40 1
C-1 or A-
3 400 40 1
C-2 400 40 2
C-3 400 40 3
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Table B.2
Effect of hydrogen pressure on product yield, selectivity and conversion of waste virgin
coconut oil cracking to biofuels through hydrocracking process over HZSM-5 as
catalyst at 400 ˚C and 1 h.
Sample Material Weight (g) Yield (wt%) Selectivity (wt%) Xl (wt%)
A-1
Feed 90.75
63.9
Gasoline 1.232 1.36 1.61
Kerosene 17.280 19.04 22.59
Diesel 39.480 43.5 51.60
Residue 18.513 20.4 24.20
A-2
Feed 90.75
64.25
Gasoline 1.540 1.7 2.02
Kerosene 17.920 19.75 23.55
Diesel 39.200 42.81 51.05
Residue 17.787 19.6 23.37
A-3
Feed 90.75
66.54
Gasoline 2.464 2.72 3.23
Kerosene 19.840 21.86 26.04
Diesel 38.080 41.96 49.99
Residue 15.792 17.4 20.73
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Table B.3
Effect of temperature on product yield, selectivity and conversion of waste virgin
coconut oil cracking to biofuels through hydrocracking process over HZSM-5 as
catalyst at 40 bar and 1 h.
Sample Material Weight (g) Yield (wt%) Selectivity (wt%) Xl
(wt%)
B-1
Feed 90.75
69.55
Gasoline 0.318 0.35 0.43
Kerosene 9.600 10.58 13
Diesel 53.200 58.62 72.06
Residue 10.709 11.8 14.51
B-2
Feed 90.75
67.13
Gasoline 0.520 0.57 0.69
Kerosene 12.800 14.11 17.05
Diesel 47.600 52.45 63.40
Residue 14.157 15.6 18.86
A-3
Feed 90.75
66.54
Gasoline 2.464 2.72 3.23
Kerosene 19.840 21.86 26.04
Diesel 38.080 41.96 49.99
Residue 15.792 17.4 20.73
Ref. code: 25605810030592YLH
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Table B.4
Effect of reaction time on product yield, selectivity and conversion of waste virgin
coconut oil cracking to biofuels through hydrocracking process over HZSM-5 as
catalyst at 400 ˚C and 40 bar.
Sample Material Weight (g) Yield (wt%) Selectivity (wt%) Xl
(wt%)
A-3
Feed 90.75
66.54
Gasoline 2.464 2.72 3.23
Kerosene 19.840 21.86 26.04
Diesel 38.080 41.96 49.99
Residue 15.792 17.4 20.73
C-2
Feed 90.75
65.64
Gasoline 2.772 3.05 3.63
Kerosene 17.600 19.39 23.08
Diesel 39.200 43.2 51.40
Residue 15.7922 18.4 21.89
C-3
Feed 90.75
65.94
Gasoline 6.160 6.79 7.86
Kerosene 28.480 31.38 36.35
Diesel 25.200 27.77 32.16
Residue 18.513 20.4 23.63
Ref. code: 25605810030592YLH
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APPENDIX C
CALCULATION
%Yield, selectivity and conversion of liquid biofuel product
Example: Calculated yield, selectivity, and conversion of waste virgin coconut oil
cracking to biofuels through hydrocracking process over HZSM-5 as catalyst
(Conditions: 400˚C, 40 bar, 1 h)
Material Weight (g) Yield (wt%) Selectivity (wt%) Xl (wt%)
Feed 90.75
66.54
Gasoline 2.464 2.72 3.23
Kerosene 19.840 21.86 26.04
Diesel 38.080 41.96 49.99
Residue 15.792 17.4 20.73
𝐶𝑜𝑛𝑣𝑒𝑟𝑠𝑖𝑜𝑛 𝑜𝑓 𝑙𝑖𝑞𝑢𝑖𝑑 𝑏𝑖𝑜𝑓𝑢𝑒𝑙 𝑝𝑟𝑜𝑑𝑢𝑐𝑡 (%) = 𝑙𝑖𝑞𝑢𝑖𝑑 𝑏𝑖𝑜𝑓𝑢𝑒𝑙 𝑝𝑟𝑜𝑑𝑢𝑐𝑡 (𝑔)
𝑖𝑛𝑖𝑡𝑖𝑎𝑙 𝑓𝑒𝑒𝑑𝑠𝑡𝑜𝑐𝑘 (𝑔)𝑥 100%
= [(2.464+19.840+38.080)/90.750] x 100
= 66.54 wt%
𝑌𝑖𝑒𝑙𝑑 𝑜𝑓 𝑑𝑖𝑒𝑠𝑒𝑙 (𝑤𝑡%) = 𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑓𝑟𝑎𝑐𝑡𝑖𝑜𝑛𝑎𝑙 𝑑𝑖𝑠𝑡𝑖𝑙𝑙𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝑙𝑖𝑞𝑢𝑖𝑑 𝑝𝑟𝑜𝑑𝑢𝑐𝑡 (𝑔)
𝑖𝑛𝑖𝑡𝑖𝑎𝑙 𝑓𝑒𝑒𝑑𝑠𝑡𝑜𝑐𝑘 (𝑔)𝑥 100%
= (38.080 /90.750) x 100
= 41.96 wt%
𝑆𝑒𝑙𝑒𝑐𝑡𝑖𝑣𝑖𝑡𝑦 𝑜𝑓 𝑑𝑖𝑒𝑠𝑒𝑙 (𝑤𝑡%) = 𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑡𝑎𝑟𝑔𝑒𝑡 𝑝𝑟𝑜𝑑𝑢𝑐𝑡 (𝑔)
𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑙𝑖𝑞𝑢𝑖𝑑 𝑝𝑟𝑜𝑑𝑢𝑐𝑡 (𝑔)𝑥 100%
= [38.080 / (2.464+19.840+38.080+15.792)] x 100
= 49.99 wt%
Ref. code: 25605810030592YLH
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APPENDIX D
PEARSON’S CORRELATION
Table D.1
Pearson’s correlation for operating parameters on gasoline production
Table D.2
Pearson’s correlation for operating parameters on kerosene production
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Table D.3
Pearson’s correlation for operating parameters on diesel production
Table D.4
Liquid biofuel yield comparison between experimental (actual) and model
predicted results
No.
Temperature Pressure Time Actual Predicted Actual Predicted Actual Predicted
(°C) (bar) (h) Yield of gasoline
(wt%)
Yield of kerosene
(wt%)
Yield of diesel
(wt%)
1 350 40 1 0.35 0.11 10.58 10.22 58.62 58.96
2 375 40 1 0.57 1.03 14.11 14.78 52.45 51.79
3 400 40 1 2.72 1.96 21.86 19.33 41.96 44.61
4 400 20 1 1.36 1.37 19.04 19.25 43.5 43.01
5 400 30 1 1.7 1.66 19.75 19.29 42.81 43.81
6 400 40 2 3.06 4.11 19.39 24.15 43.2 37.6
7 400 40 3 6.79 6.25 31.38 28.97 27.77 30.59
Ref. code: 25605810030592YLH
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APPENDIX E
PRODUCT DISTRIBUTION (BATCH REACTOR)
APPENDIX E.1: The product distribution was detected by gas-chromatography (batch
reactor)
Table E.1
The effect of initial hydrogen pressure on the product distribution and degree of
deoxygenation and degree of cracking
Sample
Hydrocarbon products Oxygenated
products Total
oxy DOD DOC
Gasoline Kerosene Diesel >C18 Trig.
acid.
Frag.
acid R-O
20 bar 0.09 4.90 6.18 0.00 87.43 0.07 1.30 88.80 11.20 12.50
30 bar 0.21 5.58 4.96 0.41 87.36 0.00 1.05 88.41 11.59 12.64
40 bar 0.14 5.86 5.53 0.00 86.36 0.06 1.60 88.01 11.99 13.59
*Trig. = triglyceride acid, Frag. = fragment acid
Ref. code: 25605810030592YLH
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Table E.2
The effect of reaction temperature on the product distribution and degree of
deoxygenation and degree of cracking
Sample
Hydrocarbon products Oxygenated
products Total
oxy DOD DOC
Gasoline Kerosene Diesel >C18 Trig.
acid.
Frag.
acid R-O
350 °C 0.59 0.00 3.56 0.19 94.32 0.50 0.00 94.82 5.18 5.18
375 °C 0.09 4.34 3.16 0.00 91.22 0.03 0.62 91.87 8.13 8.75
400 °C 0.14 5.86 5.53 0.00 86.36 0.06 1.60 88.01 11.99 13.59
*Trig. = triglyceride acid, Frag. = fragment acid
Table E.3
The effect of reaction time on the product distribution and degree of deoxygenation
and degree of cracking
Sample
Hydrocarbon products Oxygenated
products Total
oxy DOD DOC
Gasoline Kerosene Diesel >C18 Trig.
acid
Frag.
acid R-O
60
minutes 0.14 5.86 5.53 0.00 86.36 0.06 1.60 88.01 11.99 13.59
120
minutes 1.62 0.19 6.52 0.63 87.84 0.00 2.10 89.94 10.06 12.16
180
minutes 0.37 14.82 14.43 0.52 66.24 0.18 2.42 68.84 31.16 33.58
*Trig. = triglyceride acid, Frag. = fragment acid
Ref. code: 25605810030592YLH
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Table E.4
The product distribution and degree of deoxygenation and degree of cracking at the
condition no add catalyst (400 °C/40 bar/60 minutes) and no add hydrogen gas (400
°C/60 minutes)
Sample
Hydrocarbon products Oxygenated
products Total
oxy DOD DOC
Gasoline Kerosene Diesel >C18 Trig.
acid
Frag.
acid R-O
no cat. 0.18 0.00 0.11 0.29 98.68 0.00 0.14 98.82 1.18 1.32
no H2 0.45 0.00 0.45 0.00 97.49 0.90 0.15 98.54 1.46 1.61
*Trig. = triglyceride acid, Frag. = fragment acid
APPENDIX E.2: The calculation for the degree of deoxygenation and the degree of
cracking (batch reactor)
Example: Calculated the degree of deoxygenation and the degree of cracking of waste
virgin coconut oil cracking to biofuels through hydrocracking process over
HZSM-5 as catalyst (Conditions: 400˚C, 40 bar, 3 h)
Sample
Hydrocarbon products Oxygenated
products Total
oxy DOD DOC
Gasoline Kerosene Diesel >C18 Trig.
acid
Frag.
acid R-O
180
minute 0.37 14.82 14.43 0.52 66.24 0.18 2.42 68.84 31.16 33.58
*Trig. = triglyceride acid, Frag. = fragment acid
Ref. code: 25605810030592YLH
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𝑫𝒆𝒈𝒓𝒆𝒆 𝒐𝒇 𝒅𝒆𝒐𝒙𝒚𝒈𝒆𝒏𝒂𝒕𝒊𝒐𝒏 (𝑫𝑶𝑫) = (1 −𝑂𝑥𝑦𝑔𝑒𝑛𝑎𝑡𝑒𝑑𝑝𝑟𝑜𝑑𝑢𝑐𝑡
𝑂𝑥𝑦𝑔𝑒𝑛𝑎𝑡𝑒𝑑𝑓𝑒𝑒𝑑
) ∗ 100
= (1-68.84/100)*100
= 31.16 %
𝑫𝒆𝒈𝒓𝒆𝒆 𝒐𝒇 𝒄𝒓𝒂𝒄𝒌𝒊𝒏𝒈 (𝑫𝑶𝑪) = (1 −𝑐𝑎𝑟𝑏𝑜𝑥𝑦𝑙𝑖𝑐 𝑎𝑐𝑖𝑑𝑝𝑟𝑜𝑑𝑢𝑐𝑡
𝑐𝑎𝑟𝑏𝑜𝑥𝑦𝑙𝑖𝑐 𝑎𝑐𝑖𝑑𝑓𝑒𝑒𝑑) ∗ 100
= [1-(66.24+0.18)/100]*100
= 33.58 %
Ref. code: 25605810030592YLH
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APPENDIX E.3: Selectivity of product distribution
Table E.5
The selectivity of carbon atom number of liquid yield from hydrocracking process over
HZSM-5 were detected by gas-chromatography
Carbon
number
350
°C
375
°C
400
°C
20
bar
30
bar
40
bar
60
min
120
min
180
min
C7 13.51 1.13 1.22 0.76 1.89 1.22 1.22 18.10 0.34
C8 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.89
C9 0.00 5.28 4.50 2.04 0.00 4.50 4.50 0.00 4.95
C10 0.00 11.14 7.22 4.86 4.60 7.22 7.22 0.00 7.33
C11 0.00 33.39 32.40 31.44 37.55 32.40 32.40 0.00 29.27
C12 0.00 7.39 6.68 5.57 7.84 6.68 6.68 2.17 7.62
C13 38.13 17.66 17.17 16.57 19.16 17.17 17.17 26.31 16.29
C14 0.00 1.62 4.20 2.84 2.68 4.20 4.20 0.00 7.29
C15 27.89 11.78 20.98 14.23 14.19 20.98 20.98 27.72 12.83
C16 0.00 0.71 0.00 6.18 0.00 0.00 0.00 0.00 1.61
C17 13.34 7.92 5.21 14.18 8.45 5.21 5.21 11.85 5.96
C18 2.77 1.99 0.42 1.33 0.00 0.42 0.42 6.81 3.89
C19 0.00 0.00 0.00 0.00 3.64 0.00 0.00 0.00 0.00
C20 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
C21 0.00 0.00 0.00 0.00 0.00 0.00 0.00 7.04 1.72
C22 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
C23 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
C24 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
C25 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
C26 4.36 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Sum 100 100 100 100 100 100 100 100 100
Ref. code: 25605810030592YLH
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Table E.6
The distribution of aromatic, alkane, and alkene for kerosene fraction
Kerosene
fraction
350
°C
375
°C
400
°C
20
bar
30
bar
40
bar
60
min
120
min
180
min
Selectivity (%) Selectivity (%) Selectivity (%)
Aromatic 0.00 13.58 1.21 9.32 11.53 1.21 1.21 0.00 12.12
Alkane 0.00 15.75 16.80 15.57 12.55 16.80 16.80 0.00 8.57
Alkene 0.00 70.66 81.99 75.11 75.91 81.99 81.99 100.00 79.31
Ref. code: 25605810030592YLH
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APPENDIX F
PRODUCT DISTRIBUTION (CONTINUOUS PROCESS)
The product distribution was detected by gas-chromatography (continuous process)
Table F
The effect of hydrogen flow rate (ml/min) on the selectivity to product at the various
of the reaction time (°C)
Hydrogen
flow rate
(ml/min)
Reaction time (minute)
30 minutes 60 minutes 120 minutes
G K D G K D G K D
20 58.60 41.40 0.00 0.00 98.63 1.37 6.42 56.74 36.84
30 7.28 92.05 0.68 0.00 100.00 0.00 0.00 100.00 0.00
40 0.00 81.98 18.02 0.00 59.64 40.36 0.00 100.00 0.00
50 75.78 7.10 17.12 0.00 95.64 4.36 0.00 100.00 0.00
G = gasoline K =kerosene D = Diesel
Ref. code: 25605810030592YLH
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APPENDIX G
THE PROPOSED PATHWAY OF HYDROPROCESSING PROCESS (BATCH PROCESS)
Solid circles represent liquid compounds detected by GC-MS.
Dashed circles represent possible products containing in gas-phase samples which
was not collected.
Figure A.2 The proposed pathway reaction of hydroprocessing of tetradecanoic acid
Ref. code: 25605810030592YLH
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Solid circles represent liquid compounds detected by GC-MS.
Dashed circles represent possible products containing in gas-phase samples which
was not collected.
Figure A.3 The proposed pathway reaction of hydroprocessing of dodecanoic acid
Ref. code: 25605810030592YLH
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Solid circles represent liquid compounds detected by GC-MS.
Dashed circles represent possible products containing in gas-phase samples which
was not collected.
Figure A.4 The proposed pathway reaction of hydroprocessing of decanoic acid
Ref. code: 25605810030592YLH
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Solid circles represent liquid compounds detected by GC-MS.
Dashed circles represent possible products containing in gas-phase samples which
was not collected.
Figure A.5 The proposed pathway reaction of hydroprocessing of octanoic acid
Ref. code: 25605810030592YLH
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BIOGRAPHY
Name Miss Panadda Yotsomnuk
Date of Birth February 2, 1993
Educational Attainment 2015: B. Eng. (Chemical Engineering)
Silpakorn University
Scholarship Year 2015: Scholarship Thammasat University
Research Fund
Publication
Yotsomnuk, P., & Skolpap, W. (2017). Biofuel production from waste virgin coconut oil
by hydrocracking over HZSM-5 zeolite. World research library, Taipei, Taiwan,
26-27 March, 1-4. Academics World International Conference.
Ref. code: 25605810030592YLH
