renewable levulinic acid production catalyzed by...

UNIVERSITI TEKNOLOGI MALAYSIA

RENEWABLE LEVULINIC ACID PRODUCTION CATALYZED BY IRON

MODIFIED HY ZEOLITE AND FUNCTIONALIZED IONIC LIQUID

NUR AAINAA SYAHIRAH BINTI RAMLI

i

.

RENEWABLE LEVULINIC ACID PRODUCTION CATALYZED BY IRON

MODIFIED HY ZEOLITE AND FUNCTIONALIZED IONIC LIQUID

JULY 2015

Faculty of Chemical Engineering

Universiti Teknologi Malaysia

A thesis submitted in fulfilment of the

requirements for the award of the degree of

Doctor of Philosophy (Chemical Engineering)

NUR AAINAA SYAHIRAH BINTI RAMLI

iii

Verily, with every hardship comes ease (Holy Qur'an 94:6)

DEDICATION

iv

I would like to take this opportunity to express my gratitude firstly to Allah

S.W.T for His blessings and guidance. Alhamdulillah this long journey has come to

an end, where I have gained a lot of experience that are useful to me, not only from

conducting research and experiments, but also other tasks that I have performed and

accomplished throughout my stay here, directly or indirectly.

First and foremost, my sincere and gratefulness goes to my supervisor, Prof.

Dr. Nor Aishah Saidina Amin for her priceless guidance and suggestions in

supervising my research. Besides, she taught me lots in preparing international

journal papers. In the future, this knowledge will be very useful for me especially

when I involve in the academic world. Aside from that, I would like to extend my

warmest thanks to Chemical Reaction Engineering Group (CREG, UTM) members

for their support and valuable inputs regarding the research. Special thanks for those

who have helped me in the experimental works. To Prof. Dr. Taufiq Yun Hin

(UPM), Prof. Dr. Salasiah Endud (UTM), Mr Ismail, Mr. Latfi, and Mrs. Zainab,

thank you very much for assisting me in the analysis of products and characterization

of catalysts.

I also wish to express my gratitude and utmost appreciation to my beloved

parents, my father Mr. Ramli Mohd Ali and my mom Mrs. Saripah Marwan for being

with me through this journey. Last but not least, I would also like to gratefully

acknowledge the financial support in the form of MyPhD scholarship by the Ministry

of Education (MOE).

ACKNOWLEDGEMENT

v

Levulinic acid is a versatile platform chemical that can be derived from

biomass as an alternative to fossil fuel resources. In this study, a series of

heterogeneous iron modified HY zeolites (Fe/HY zeolite): 5% Fe/HY, 10% Fe/HY,

15% Fe/HY, and homogeneous functionalized ionic liquids (FIL): 1-butyl-3-

methylimidazolium tetrachloroferrate ([BMIM][FeCl4]), 1-sulfonic acid-3-

methylimidazolium chloride ([SMIM][Cl]), 1-sulfonic acid-3-methylimidazolium

tetrachloroferrate ([SMIM][FeCl4]), were synthesized, characterized, and tested as a

catalyst for glucose conversion to levulinic acid. The properties of Fe/HY zeolite

were characterized using x-ray diffraction (XRD), field emission scanning electron

microscopy - energy dispersive x-ray (FESEM-EDX), x-ray fluorescence (XRF),

Fourier transform infrared spectroscopy (FTIR), nitrogen (N2) physisorption, thermal

gravimetric analysis (TGA), temperature programmed desorption of ammonia (NH3-

TPD), and pyridine-FTIR. The synthesized FIL were characterized using carbon,

hydrogen, nitrogen, and sulfur (CHNS) elemental analysis and carbon-13 and proton

nuclear magnetic resonance (13

C and 1H NMR). The acidic properties of FIL were

examined using pyridine-FTIR, Hammett function, and acid-base titration.

Experimental results indicated that the selective Fe/HY zeolite and FIL for levulinic

acid production from glucose were 10% Fe/HY and [SMIM][FeCl4], with 62% yield

at 180 °C for 3 h, and 68% yield at 150 °C for 4 h, respectively. For Fe/HY zeolite,

catalyst with large surface area, high concentration of acid sites and appropriate ratio

of Brønsted to Lewis acids seemed suitable for levulinic acid production. It was also

discovered FIL which contained both Brønsted and Lewis acid sites, offered a good

catalytic performance. Optimization of levulinic acid yield from glucose and oil

palm fronds (OPF) were conducted using the response surface methodology (RSM).

At optimum conditions, 61.8% and 19.6% of levulinic acid yields were attained from

glucose and OPF, respectively, over 10% Fe/HY zeolite. Meanwhile, by using

[SMIM][FeCl4] 69.2% and 24.8% of levulinic acid yields were produced from

glucose and OPF, respectively. Both catalysts can be reused without significant loss

of catalytic activity. Kinetic studies of glucose conversion to levulinic acid were

performed using both 10% Fe/HY zeolite and [SMIM][FeCl4]. The kinetic

parameters obtained were lower and comparable with previous catalysts employed in

glucose conversion to levulinic acid. This study demonstrated the potential of

proposed catalysts to be used in a biorefinery for processing renewable feedstocks at

mild process conditions.

ABSTRACT

vi

Asid levulinik adalah bahan kimia asas serba guna yang dapat dihasilkan

daripada biojisim sebagai alternatif kepada sumber bahan api fosil. Dalam kajian ini,

satu siri zeolit HY terubahsuai ferum heterogen (zeolit Fe/HY): 5% Fe/HY, 10%

Fe/HY, 15% Fe/HY, dan cecair ionik kumpulan fungsian homogen (FIL): 1-butil-3-

metilimidazolium tetrakloroferat ([BMIM][FeCl4]), 1-asid sulfonik-3-

metilimidazolium klorida, ([SMIM][Cl]), 1-asid sulfonik-3-metilimidazolium

tetrakloroferat ([SMIM][FeCl4]), disintesis, dicirikan, dan diuji sebagai pemangkin

untuk penukaran glukosa kepada asid levulinik. Pencirian sifat-sifat zeolit Fe/HY

dilakukan menggunakan pembelauan sinar-x (XRD), mikroskopi elektron pengimbas

pancaran medan - sebaran sinar-x (FESEM-EDX), pendarfluor sinar-x (XRF),

spektroskopi inframerah transformasi Fourier (FTIR), penjerapan fizik nitrogen (N2),

analisis gravimetri terma (TGA), penyahjerapan berprogram suhu ammonia (NH3-

TPD), dan FTIR-piridina. FIL yang telah disintesis dicirikan menggunakan analisis

unsur karbon, hidrogen, nitrogen, dan sulfur (CHNS) dan resonans magnet nukleus

karbon-13 dan proton (13

C dan 1H NMR). Sifat berasid bagi FIL dikaji

menggunakan FTIR-piridina, fungsi Hammett, dan pentitratan asid-bes. Keputusan

eksperimen menunjukkan bahawa zeolit Fe/HY dan FIL yang selektif bagi

penghasilan asid levulinik daripada glukosa adalah 10% Fe/HY dan [SMIM][FeCl4],

masing-masing dengan hasil sebanyak 62% pada suhu 180 °C selama 3 j, dan hasil

sebanyak 65% pada 150 °C selama 4 j. Untuk zeolit Fe/HY, pemangkin dengan luas

permukaan yang besar, kepekatan yang tinggi bagi tapak asid dan nisbah yang sesuai

untuk asid Lewis hingga Brønsted tampak sesuai untuk penghasilan asid levulinik.

Kajian juga menemukan FIL yang mengandungi kedua-dua tapak asid Lewis dan

Brønsted memberikan prestasi pemangkinan yang baik. Pengoptimuman hasil asid

levulinik daripada glukosa dan pelepah sawit (OPF) telah dilakukan menggunakan

kaedah gerak balas permukaan (RSM). Pada keadaan optimum, hasil asid levulinik

sebanyak 61.8% dan 19.6% masing-masing telah dicapai daripada glukosa dan OPF,

menggunakan 10% zeolit Fe/HY. Sementara itu, dengan menggunakan

[SMIM][FeCl4], sebanyak 64.2% dan 24.3% asid levulinik masing-masing telah

dihasilkan daripada glukosa dan OPF. Kedua-dua pemangkin dapat digunakan

semula tanpa kehilangan aktiviti katalitik yang signifikan. Kajian kinetik penukaran

glukosa kepada asid levulinik telah dilakukan menggunakan kedua-dua 10% zeolit

Fe/HY dan [SMIM][FeCl4]. Parameter kinetik yang diperoleh adalah lebih rendah

dan setanding dengan pemangkin sebelumnya yang digunakan dalam penukaran

glukosa kepada asid levulinik. Kajian ini menunjukkan potensi pemangkin yang

dicadangkan sesuai digunakan dalam loji biopenapisan minyak untuk memproses

stok suapan boleh diperbaharu pada keadaan proses yang sederhana.

ABSTRAK

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TABLE OF CONTENTS

CHAPTER

TITLE PAGE

DECLARATION ii

DEDICATION iii

ACKNOWLEDGEMENT iv

ABSTRACT v

ABSTRAK vi

TABLE OF CONTENTS vii

LIST OF TABLES xii

LIST OF FIGURES xv

LIST OF ABBREVATIONS xxiv

LIST OF SYMBOLS xxvi

LIST OF APPENDICES xxvii

1 INTRODUCTION 1

1.1 Research Background 1

1.2 Problem Statement 5

1.3 Research Hypotheses 9

1.4 Research Objectives 10

1.5 Scopes of Research 11

1.6 Research Significance 12

1.7 Thesis Outline 13

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viii

2 LITERATURE REVIEW 14

2.1 Lignocellulosic Biomass Feedstock 14

2.1.1 Fractionation of Lignocellulosic Biomass Feedstock 15

2.1.2 Oil Palm Fronds 18

2.2 Levulinic Acid 20

2.2.1 Levulinic Acid Production 22

2.2.2 Levulinic Acid Applications and Derivatives 26

2.2.3 Mechanism and Scheme for Levulinic Acid Production 28

2.2.4 Homogeneous Acid Catalysis 33

2.2.5 Heterogeneous Acid Catalysis 37

2.3 Modified Zeolite 42

2.3.1 Zeolite and Modified Zeolite 42

2.3.2 Zeolite for Levulinic Acid Production 44

2.4 Functionalized Ionic Liquid Catalyst 49

2.4.1 Ionic Liquid and Functionalized Ionic Liquid 49

2.4.2 Ionic Liquid for Biomass Processing 51

2.4.3 Ionic Liquid for Levulinic Acid Production 53

2.5 Factors Influencing the Levulinic Acid Production 59

2.6 Characterizations of Catalyst 66

2.7 Optimization by Response Surface Methodology 68

2.8 Kinetic Study of Glucose Conversion to Levulinic Acid 70

2.9 Summary of the Chapter 79

3 RESEARCH METHODOLOGY 81

3.1 Overall Research Methodology 81

3.2 Materials 88

3.3 Fe/HY Zeolite Catalyst 89

ix

3.3.1 Catalyst Preparation 89

3.3.2 Catalyst Characterizations 90

3.4 Functionalized Ionic Liquid Catalyst 93

3.4.1 Catalyst Preparation 93

3.4.2 Catalyst Characterization 96

3.5 Characterization of Oil Palm Fronds 98

3.6 Catalytic Runs 99

3.6.1 Fe/HY Zeolite Catalyst 99

3.6.2 Functionalized Ionic Liquid Catalyst 100

3.7 Optimization of Levulinic Acid Production from Glucose

and Oil Palm Fronds Conversions 101

3.7.1 Design of Experiments 101

3.7.2 Data Analysis and Optimization 104

3.8 Kinetic Study of Glucose Conversion to Levulinic Acid 106

3.9 Product Analysis 109

4 LEVULINIC ACID PRODUCTION OVER IRON

MODIFIED HY ZEOLITE CATALYST 112

4.1 Introduction 112

4.2 Catalyst Preparation 113

4.3 Catalyst Characterizations 114

4.3.1 X-Ray Diffraction (XRD) 114

4.3.2 Field Emission Scanning Electron Microscopy -

Electron Dispersive X-ray (FESEM-EDX) and X-ray

Fluorescence (XRF) 117

4.3.3 Nitrogen (N2) Physisorption 119

4.3.4 Fourier Transform Infrared Spectroscopy (FTIR) 122

4.3.5 Thermal Gravimetric Analysis (TGA) 123

x

4.3.6 Temperature Programmed Desorption of Ammonia

(NH3-TPD) 125

4.3.7 Pyridine Adsorption 128

4.4 Glucose Conversion to Levulinic Acid 129

4.4.1 Catalyst Screening and Performance 129

4.4.2 Optimization of Levulinic Acid Production from

Glucose Conversion 150

4.5 Oil Palm Fronds Conversion to Levulinic Acid 160

4.5.1 Oil Palm Fronds Characterization 160

4.5.2 Catalyst Testing 162

4.5.3 Optimization of Levulinic Acid Production from Oil

Palm Fronds Conversion 167


5 LEVULINIC ACID PRODUCTION OVER

FUNTIONALIZED IONIC LIQUID CATALYST 179


5.2 Catalyst Preparation 180

5.3 Catalyst Characterization 182

5.3.1 CHNS Elemental Analysis 182

5.3.2 1H and 13C Nuclear Magnetic Resonance (NMR) 182

5.3.3 Pyridine FTIR 183

5.3.4 Hammett (Ho) Acidity Function 184

5.3.5 Acid Base Titration 184

5.4 Glucose Conversion to Levulinic Acid 184

5.4.1 Catalyst Screening and Performance 184

5.4.2 Optimization of Levulinic Acid Production from

Glucose Conversion 198

xi

5.5 Oil Palm Fronds Conversion to Levulinic Acid 207

5.5.1 Catalyst Testing 207

5.5.2 Optimization of Levulinic Acid Production from Oil

Palm Fronds Conversion 213


6 KINETIC STUDY OF GLUCOSE CONVERSION TO

LEVULINIC ACID 224


6.2 Fe/HY zeolite 227

6.2.1 Effect of External and Internal Diffusions 228

6.2.2 Effect of Reaction Temperature 230

6.2.3 Kinetic Study 233

6.3 Functionalized Ionic Liquid 239

6.3.1 Effect of Reaction Temperature 239

6.3.2 Kinetic Study 242

6.4 Comparison with Previous Kinetic Models 247


7 CONCLUSION 255

7.1 Conclusions 255

7.2 Recommendations 258

REFERENCES 260

Appendices A - H 282 – 305

xii

LIST OF TABLES

TABLE NO.

TITLE PAGE

2.1 Composition of selected lignocellulosic biomass

feedstock (Rackemann and Doherty, 2011). 16

2.2 Source of lignocellulosic biomass waste in Malaysia

(Goh et al., 2010). 19

2.3 Chemical compositions of oil palm parts (wt%) (Shibata

et al., 2008). 20

2.4 Properties of levulinic acid (Timokhin et al., 1999). 21

2.5 Properties of 5-HMF (Mukherjee et al., 2015). 21

2.6 Homogenous acid catalysis for the production of

levulinic acid and the intermediate compound; 5-HMF. 35

2.7 Heterogeneous acid catalysis for the production of

levulinic acid and the intermediate compound; 5-HMF. 38

2.8 The use of zeolites for catalytic production of levulinic

acid and the intermediate product; 5-HMF. 45

2.9 The use of ionic liquids for catalytic production of

levulinic acid and the intermediate product; 5-HMF. 55

2.10 Kinetic study of glucose conversion to levulinic acid. 74

2.11 Kinetic study of fructose conversion to levulinic acid. 76

2.12 Kinetic study of cellulose/lignocellulosic biomass

conversion to levulinic acid. 77

xiii

2.13 Kinetic study of 5-HMF conversion to levulinic acid. 78

3.1 Experimental range and factor level of process variables

tested for glucose conversion using the selected Fe/HY

zeolite catalyst. 102


tested for glucose conversion using the selected FIL

catalyst. 102


tested for OPF conversion using the selected Fe/HY



tested for OPF conversion using the selected FIL catalyst. 103

3.5 Experimental design of four parameters based on Box-

Behnken design. 103

4.1 Composition of elements present in HY and Fe/HY

zeolite catalysts from EDX. 117

4.2 Composition of elements present in HY and Fe/HY

zeolite catalysts from XRF. 117

4.3 Surface area and porosity of HY zeolite and Fe/HY

zeolite catalysts. 121

4.4 Acidity of HY zeolite and Fe/HY zeolite catalysts. 127

4.5 Comparison of different catalysts for glucose conversion

to levulinic acid. 141

4.6 Reusability of 10% Fe/HY zeolite for glucose conversion

to levulinic acid. 147

4.7 Experimental data set and corresponding experimental

and predicted levulinic acid yields from glucose using

10% Fe/HY zeolite catalyst. 150

4.8 Analysis of variance (ANOVA) for quadratic model of

levulinic acid yield from glucose using 10% Fe/HY


xiv

4.9 OPF compositions from TGA and LAP methods. 161

4.10 Levulinic acid production using various lignocellulosic

biomass feedstocks and catalysts. 166


and predicted levulinic acid yields from OPF using 10%

Fe/HY zeolite catalyst. 167


levulinic acid yield from OPF using 10% Fe/HY zeolite

catalyst. 169

5.1 Comparison of different ionic liquids as catalyst for

glucose conversion reaction. 196


and predicted levulinic acid yield from glucose using

[SMIM][FeCl4] catalyst. 198


levulinic acid yield from glucose using [SMIM][FeCl4]

catalyst. 200

5.4 Levulinic acid production using various lignocellulosic

biomass feedstocks and catalysts. 210


and predicted levulinic acid yields from OPF using



levulinic acid yield from OPF using [SMIM][FeCl4]

catalyst. 215

6.1 Kinetic parameters of glucose conversion using 10%

Fe/HY zeolite catalyst. 237

6.2 Kinetic parameters of glucose conversion using


6.3 Kinetic study of glucose conversion to levulinic acid. 251

xv

LIST OF FIGURES

FIGURE NO.

TITLE PAGE

1.1 World consumption of fossil resources 1990–2040

(Girisuta, 2007). 2

1.2 Top building block chemicals derived from biomass

feedstock (Werpy et al., 2004). 3

1.3 Potential uses of levulinic acid (Rackemann and Doherty,

2011). 4

1.4 Reaction scheme for the conversion of lignocellulosic

biomass to levulinic acid (Girisuta, 2007). 5

2.1 Conversion of biomass derived feedstock for production

of various biofuels and chemicals (Alonso et al., 2010). 15

2.2 Location and arrangement of cellulose, hemicellulose,

and lignin in lignocellulosic biomass (Murphy and

McCarthy, 2005). 16

2.3 A cellulose chain (A) and hydrogen bonds present in

cellulose (B) (Olivier-Bourbigou et al., 2010). 17

2.4 Various parts of oil palm. 19

2.5 Levulinic acid structure. 20

2.6 5-HMF structure. 21

2.7 Simplified schematic stage of a biomass refinery concept

(Girisuta, 2007). 23

xvi

2.8 Levulinic acid production routes; petrochemical refinery

and biomass refinery. Adapted from Lucia et al. (2006). 24

2.9 Chemical conversion of cellulose to levulinic acid in the

Biofine process (Hayes et al., 2008). 25

2.10 Levulinic acid derivatives (Girisuta, 2007). 26

2.11 5-HMF derivatives (Gallezot, 2012). 28

2.12 Simplified reaction pathway of glucose conversion to

levulinic acid. 29

2.13 Proposed mechanism of fructose conversion to 5-HMF

(Caratzoulas and Vlachos, 2011). 30

2.14 Proposed mechanism for conversion of 5-HMF to

levulinic acid (Girisuta, 2007; Horvat et al., 1985). 31

2.15 Reaction scheme of lignocellulosic biomass conversion to

levulinic acid (Rackemann and Doherty, 2011). 32

2.16 Decomposition of cellulose to glucose. 33

2.17 Basic zeolite structure. 42

2.18 Commonly used anions and cations in ionic liquids. 50

2.19 General steps for ionic liquid-catalyst recycle process for

biomass derived carbohydrate conversion to 5-HMF and

levulinic acid. Adapted from Chinnappan et al., 2014;

Tao et al., 2011b; and Tao et al., 2014. 58

2.20 Comparison of molecular dimensions of typical feedstock

and product involved in levulinic acid production (Kruger

et al., 2012). 63

2.21 Flow chart of RSM study. Adapted from Wan Omar and

Saidina Amin (2011). 69

2.22 Reaction scheme for kinetic models of levulinic acid

production. 71

2.23 General overview of research. 80

3.1 Overall research methodology (Part 1 – 4). 82

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xvii

3.2 Research methodology - Part 1a. 83

3.3 Research methodology - Part 1b. 84

3.4 Research methodology - Part 2. 85



3.7 OPF. 88

3.8 Materials involved in the preparation of Fe/HY zeolite

catalyst; HY zeolite (a), solution of HY zeolite and FeCl3

mixture (b). 90

3.9 Materials involved in the preparation of [BMIM][FeCl4];

[BMIM][Cl] (a), mixture of [BMIM][Cl] and FeCl3.6H2O

(b). 94

3.10 Materials involved in the preparation of [SMIM][Cl];

mixture of 1-methylimidazole and CH2Cl2 (a), after

addition of SO3HCl, and layers formed before

decantation of CH2Cl2. 95

3.11 Materials involved in the preparation of

([SMIM][FeCl4]); [SMIM][Cl] (a), mixture of

[SMIM][Cl] and FeCl3.6H2O (b). 95

3.12 Experimental setup for Fe/HY zeolite catalytic testing. 99

3.13 Experimental setup for catalytic testing of FIL. 100

3.14 Reaction scheme for glucose conversion to levulinic acid. 107

4.1 Fe/HY zeolite catalysts; 5% Fe/HY zeolite (a), 10%

Fe/HY zeolite (b), and 15% Fe/HY zeolite (c). 114

4.2 XRD patterns of HY zeolite and Fe/HY zeolite catalysts

(* - peaks assigned to FAU structure, ↓ - peak assigned to

Fe2O3). 115

4.3 FESEM images of HY zeolite and Fe/HY zeolite

catalysts at 3,500× and 5,000× magnifications. 118

4.4 N2 adsorption-desorption isotherm of HY zeolite and

Fe/HY zeolite catalysts. 120

xviii

4.5 FTIR spectra of HY zeolite and Fe/HY zeolite catalysts. 123

4.6 TGA (a) and DTG (b) curves of HY zeolite and Fe/HY

zeolite catalysts. 124

4.7 NH3-TPD profiles of HY zeolite and Fe/HY zeolite

catalysts. 126

4.8 FTIR spectra of pyridine adsorbed on HY zeolite and

Fe/HY zeolite catalysts. 129

4.9 Product yields versus reaction temperature for 5% Fe/HY

zeolite (a), 10% Fe/HY zeolite (b), and 15% Fe/HY

zeolite (c) catalysts (1 g glucose, 1 g Fe/HY zeolite

catalyst, 50 mL water, 3 h). 130

4.10 Glucose conversion and levulinic acid selectivity versus

reaction temperature for 5% Fe/HY zeolite (a), 10%

Fe/HY zeolite (b), and 15% Fe/HY zeolite (c) catalysts (1

g glucose, 1 g Fe/HY zeolite catalyst, 50 mL water, 3 h). 132

4.11 Levulinic acid yield distribution with number of acid sites

(a) and ratio of Brønsted to Lewis acid sites (b) for HY

zeolite and Fe/HY zeolite catalysts (1 g glucose, 1 g

zeolite catalyst, 50 mL water, 3 h, 180 °C). 135

4.12 Levulinic acid yield versus hierarchical factor (a), and

relative microporosity versus relative mesoporosity (b) (1

g glucose, 1 g zeolite catalyst, 50 mL water, 3 h, 180 °C). 137

4.13 Effect of reaction time (a) and catalyst loading (b) on

glucose conversion, levulinic acid yield, and levulinic

acid selectivity using 10% Fe/HY zeolite catalyst. 139

4.14 Effect of glucose to water ratio on levulinic acid yield

using 10% Fe/HY zeolite catalyst (1:1 of glucose:10%

Fe/HY zeolite, 50 mL water, 3 h, 170 °C). 140

4.15 Proposed reaction mechanism of levulinic acid

production from glucose over Fe/HY zeolite catalyst.

Adapted from Utami and Amin, 2013; Zhao et al., 2007;

xix

Román-Leshkov et al., 2010; Caratzoulas and Vlachos,

2011. 143

4.16 Proposed reaction mechanism of glucose conversion to

levulinic acid over Fe/HY zeolite catalysts. (1) Glucose

isomerizes to fructose, (2) monosaccharide to 1,2-enediol,

(3) 1,2-enediol dehydrates to 5-HMF and (4) 5-HMF

rehydrates to levulinic acid and formic acid. Adapted

from Agirrezabal-Telleria et al., 2014; Jow et al., 1987;

Lourvanij and Rorrer, 1993; Kruger et al., 2012. 145

4.17 Reusability of 10% Fe/HY zeolite for glucose conversion. 147

4.18 Fresh (a) and regenerated (b) 10% Fe/HY zeolite

catalysts. 147

4.19 XRD patterns (a), FTIR spectra (b), and FESEM images

(c) of fresh and regenerated 10% Fe/HY zeolite catalyst. 149

4.20 Parity plot of levulinic acid yield from glucose

conversion using 10% Fe/HY zeolite catalyst. 153

4.21 Pareto chart of levulinic acid yield from glucose


4.22 Response fitted surface area plots of levulinic acid yield

versus reaction temperature and reaction time. 156


versus reaction temperature and glucose loading. 157


versus reaction temperature and 10% Fe/HY zeolite

loading. 157


versus reaction time and glucose loading. 158


versus reaction time and 10% Fe/HY zeolite loading. 158


versus glucose loading and 10% Fe/HY zeolite loading. 159

xx

4.28 TGA curve of OPF. 161

4.29 Effect of reaction time on levulinic acid yield from OPF


4.30 Reusability of 10% Fe/HY zeolite catalyst for levulinic

acid production from OPF conversion. 164

4.31 Parity plot of levulinic acid yield from OPF conversion

using 10% Fe/HY zeolite catalyst. 170

4.32 Pareto chart of levulinic acid yield from OPF conversion

using 10% Fe/HY zeolite catalyst. 171




versus reaction temperature and 10% Fe/HY zeolite

loading. 174


versus reaction temperature and OPF loading. 174


versus reaction time and 10% Fe/HY zeolite loading. 175


versus reaction time and OPF loading. 175


versus OPF loading and 10% Fe/HY zeolite loading. 176

5.1 The prepared FIL catalysts; [BMIM][FeCl4] (a),

[SMIM][Cl] (b), and [SMIM][FeCl4] (c). 180

5.2 The addition of ions involved in the preparation of

[BMIM][FeCl4] (a), [SMIM][Cl] (b), and [SMIM][FeCl4]

(c). 181

5.3 Pyridine-FTIR spectra of FIL catalysts. 183

5.4 Effect of reaction temperature and time on glucose

conversion using [BMIM][FeCl4] (a), [SMIM][Cl] (b),

and [SMIM][FeCl4] (c) as catalysts. ■170 °C, ▲150 °C,

xxi

●130 °C, ×110 °C (0.1 g glucose, 10 g FIL catalyst, 10

mL water). 186

5.5 Effect of reaction temperature and time on 5-HMF (a)

and levulinic acid (b) yield using [BMIM][FeCl4] as

catalyst ■ 170 °C, ▲150 °C, ●130 °C, ×110 °C (0.1 g

glucose, 10 g FIL catalyst, 10 mL water). 189

5.6 Effect of reaction temperature and time on 5-HMF (b)

and levulinic acid (b) yield using [SMIM][Cl] as catalyst

■ 170 °C, ▲150 °C, ●130 °C, ×110 °C (0.1 g glucose, 10

g FIL catalyst, 10 mL water). 190

5.7 Effect of reaction temperature and time on 5-HMF (a)

and levulinic acid (b) yield using [SMIM][FeCl4] as

catalyst ■ 170 °C, ▲150 °C, ●130 °C, ×110 °C (0.1 g

glucose, 10 g FIL catalyst, 10 mL water). 191

5.8 Effect of glucose loading on glucose conversion and 5-

HMF and levulinic acid yield using [SMIM][FeCl4] as

catalyst (10 g FIL catalyst, 10 mL water, 150 °C, 4 h). 193

5.9 Effect of catalyst loading (a) and ratio of water to catalyst

loading (b) on glucose conversion and 5-HMF and

levulinic acid yield using [SMIM][FeCl4] as catalyst (10

mL water, 150 °C, 4 h (a), 5 g FIL catalyst, 150 °C, 4 h

(b)). 194

5.10 Reusability of [SMIM][FeCl4] for glucose conversion

reaction. 197

5.11 Fresh (a), and regenerated (b) [SMIM][FeCl4] catalysts. 197

5.12 Parity plot of levulinic acid yield from glucose using


5.13 Pareto chart of levulinic acid yield from glucose using




xxii


versus reaction temperature and glucose loading. 204


versus reaction temperature and [SMIM][FeCl4] loading. 205


versus reaction time and [SMIM][FeCl4] loading. 205


versus reaction time and glucose loading. 206


versus glucose loading and [SMIM][FeCl4] loading. 206

5.20 Reusability of [SMIM][FeCl4] catalyst for levulinic acid

production from OPF. 208

5.21 Proposed reaction scheme of levulinic acid production

using [SMIM][FeCl4] as catalyst. 212

5.22 Parity plot of levulinic acid yield from OPF using


5.23 Pareto chart of levulinic acid yield from OPF using





versus reaction temperature and OPF loading. 219


versus reaction temperature and [SMIM][FeCl4] loading. 219


versus reaction time and [SMIM][FeCl4] loading. 220


versus reaction time and OPF loading. 220


versus OPF loading and [SMIM][FeCl4] loading. 221

6.1 Reaction scheme for glucose conversion to levulinic acid. 225

xxiii

6.2 Effect of (a) agitation speed; ■ 0 rpm, ● 50 rpm, ▲ 100

rpm, □ 200 rpm, ○ 300 rpm, and (b) 10% Fe/HY zeolite

particle sizes; (● 0.18 mm, ▲ 0.21 mm, □ 0.25 mm, ○

0.30 mm) on glucose conversion. 230

6.3 Glucose decomposition using 10% Fe/HY zeolite - effect

of reaction temperature ■ 120 °C, ▲ 140 °C, ● 160 °C, *

180 °C, ○ 200 °C. 232

6.4 5-HMF decomposition using 10% Fe/HY zeolite - effect

of reaction temperature on 5-HMF conversion and LA

yield. ■ 120 °C, ▲ 140 °C, ● 160 °C, * 180 °C, ○ 200

°C. 233

6.5 Typical concentration profile of glucose decomposition

using 10% Fe/HY zeolite at 180 °C. ▲ Glucose, ● 5-

HMF, □ LA. 234

6.6 -ln(1-X) versus time for (a) glucose conversion and (b) 5-

HMF conversion using 10% Fe/HY zeolite. ■ 120 °C, ▲

140 °C, ● 160 °C, * 180 °C, ○ 200 °C. 236

6.7 Arrhenius plots of ln k versus 1/T using 10% Fe/HY

zeolite. 238

6.8 Glucose decomposition using [SMIM][FeCl4] - effect of

reaction temperature. ■ 110 °C, ▲ 130 °C, ● 150 °C, *

170 °C. 241

6.9 5-HMF decomposition using [SMIM][FeCl4] - effect of

reaction temperature. ■ 110 °C, ▲ 130 °C, ● 150 °C, *

170 °C. 242

6.10 Typical concentration profile of glucose decomposition

using [SMIM][FeCl4] at 170 °C. ▲ Glucose, ● 5-HMF, □

levulinic acid. 243

6.11 -ln(1-X) versus time for glucose conversion and 5-HMF

conversion using [SMIM][FeCl4]. ■ 110 °C, ▲ 130 °C, ●

150 °C, * 170 °C. 245

6.12 Arrhenius plots of ln k versus 1/T using [SMIM][FeCl4]. 247

xxiv

LIST OF ABBREVATIONS

5-HMF - 5-hydroxymethyl furfural

[BMIM][Cl] - 1-butyl-3-methyl imidazolium chloride

[BMIM][FeCl4] - 1-butyl-3-methyl tetrachloroferrate

[SMIM][Cl] - 1-sulfonic acid-3-methyl imidazolium chloride

[SMIM][FeCl4] - 1-sulfonicacid-3-methylimidazolium

tetrachloroferrate

AlCl3 - Aluminium (III) chloride

ANOVA - Analysis of variance

BET - Brunauer Emmett Teller

BJH - Barrett Joyner Halenda

CH2Cl2 - Dichloromethane

CrCl2 - Chromium (II) chloride

CrCl3 - Chromium (III) chloride

DMF - Dimethyl formamide

DMSO - Dimethyl sulfoxide

DNS - 3,5-dinitrosalicylic acid

FeCl2 - Iron (II) chloride

FeCl3 - Iron (III) chloride

Fe2O3 - Iron (III) oxide

FIL - Functionalized ionic liquid

GVL - γ-valerolactone

HF - Hierarchical factor

HPLC - High performance liquid chromatography

HY - Faujasite type zeolite

xxv

FESEM - Field emission scanning electron microscopy

FTIR - Fourier transform infrared spectroscopy

H2SO4 - Sulfuric acid

HCl - Hydrochloric acid

HBr - Hydrobromic acid

IR - Infrared

KBr - Potassium bromide

LAP - Laboratory analytical procedure

MIBK - Methyl isobutyl ketone

MnCl2 - Manganese (II) chloride

NaOH - Sodium hydroxide

NH3 - Ammonia

NH3-TPD - Temperature programmed desorption of ammonia

NH4Cl - Ammonium chloride

OPF - Oil palm fronds

RSM - Response surface methodology

Si - Silica

SnCl4 - Tin (IV) chloride

SO3H - Sulfonic acid

SO3HCl - Chloro sulfonic acid

TGA - Thermal gravimetric analysis

TOF - Turnover frequency

UV - Ultraviolet

XRD - X-ray diffraction

XRF - X-ray fluorescence

XPS - X-ray photoelectron spectroscopy

xxvi

LIST OF SYMBOLS

° - Degree

°C - Degree Celcius

% - Percentage

A - Pre-exponential factor

Å - Angstrom

Ea - Activation energy

g - Gram

h - Hour

Ho - Hammett acidity function

J - Joules

K - Kelvin

k - Reaction rate constant

min - Minutes

mL - Mililiter

mM - Milimolar

ppm - Parts per million

R2 - Coefficient of determination

µm - Micrometer

xxvii

LIST OF APPENDICES

APPENDIX

TITLE PAGE

A List of publications 282

B LAP procedure 284

C Fe/HY zeolite characterization 288

D Functionalized ionic liquid characterization 290

E Calibration curve 294

F Preliminary testing using HY zeolite 296

G Response surface methodology 297

H Kinetic study 298

260

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renewable levulinic acid production catalyzed by...

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