SUPERVISOR S DECLARATION

Transcription

1 SUPERVISOR S DECLARATION We hereby declare that we have checked this thesis and in our opinion, this thesis is adequate in terms of scope and quality for the award of the degree of Master of Engineering (Chemical). Signature : Name of Supervisor : Prof. Dr. Abdurahman Hamid Nour Position : Professor Date : 25 th October 2016 Signature : Name of Co-supervisor : Dr. Ramesh Kanthasamy Position : Senior Lecturer Date : 25 th October 2016

2 STUDENT S DECLARATION I hereby declare that the work in this thesis is my own except for the quotations and summaries which have been duly acknowledged. The thesis has not been accepted for any degree and is not concurrently submitted for award of other degree. Signature Name : Nitthiyah A/P Jeyaratnam ID Number : MKC Date : 25 th October 2016

3 A COMPARATIVE STUDY OF CINNAMOMUM CASSIA (CINNAMON) BARK OIL EXTRACTION THROUGH HYDRODISTILLATION (HD) AND MICROWAVE ASSISTED HYDRODISTILLATION (MAHD) NITTHIYAH A/P JEYARATNAM Thesis submitted in fulfilment of the requirements for the award of the degree of Master of Engineering (Chemical) Faculty of Chemical and Natural Resources Engineering UNIVERSITI MALAYSIA PAHANG October 2016

4 Dedicated to the Glory of The Almighty God and to My lovely parents. ii

5 ACKNOWLEDGEMENT First and foremost, I would like to profess my gratefulness to the Almighty God for the sound health and overall wellbeing during the course of my research work and thesis writing. Also, my appreciation goes to every individual who have contributed to this research in one way or the other. Firstly, my deepest gratitude is to my advisor, Prof. Dr. Abdurahman Hamid Nour for the continuous motivation and support for my master study and other related research work. I acknowledge his patience and immense knowledge which helped all through. I would also like to thank my co-supervisor, Dr. Ramesh, who has been always there to listen and give good piece of advices. I say a very big thank you sir. I am also very much indebted to my parents and my siblings for their continuous belief in me and the support they offered especially in terms of love, financial, spiritual and otherwise. I really appreciate their patience with me during my entire study in UMP. I am particularly grateful to my dear friend John Olabode Akindoyo for his prayers, great faith in me, continuous encouragement and guidance which have helped me to identify myself and my potential. Also, I really appreciate the contributions of my dearest and kind senior Ranitha and lovely junior Komathi for their support in every kind, stimulating discussions, for the sleepless nights we shared working together throughout this course. I say you are simply the best, thanks a lot. I would like to acknowledge Assoc. Prof. Dr. Azwina, Dr. Azhari Hamid Nour, Assoc. Prof. Dr. Dalour Beg, Assoc. Prof. Dr. Jolius, Assoc. Prof. Dr. Ahmad Ziad and Assoc. Prof. Dr. Ir. Said Nurdin for numerous discussions, comments and lectures on related topics that helped me improve my knowledge in the area of my research. I am also thankful for the efforts of the JPs in FKKSA laboratory, UMP especially Madam Hafizah Ramli, Mr.Razak, Mr.Hafiz and all others. Many friends have helped me stay sane through these difficult years. Their support and care helped me overcome setbacks and stay focused on my graduate study. I greatly value their friendship and I deeply appreciate their belief in me. I love you all. Finally, I would like to appreciate the financial support from UMP that funded this research work through PGRS (GRS150327). The Author. iii

6 TABLE OF CONTENTS DECLARATION TITLE PAGE DEDICATION ACKNOWLEDGEMENT ABSTRACT TRANSLATION OF ABSTRACT TABLE OF CONTENTS LIST OF TABLES LIST OF FIGURES LIST OF SYMBOLS LIST OF ABBREVIATIONS LIST OF APPENDICES ii iii iv v vi x xii xvi xvii xix CHAPTER 1 INTRODUCTION Background of Study Problem Statement Objectives Scope of Study CHAPTER 2 LITERATURE REVIEW 2.1 Introduction Cinnamomum Cassia Cinnamomum Cassia Essential Oil Conventional Methods of Essential Oil Extraction Hydrodistillation Basic Principles of Hydrodistillation Non-Conventional Methods of Essential Oil Extraction Ultrasound-Assisted Extraction Supercritical Fluid Extraction vi

7 2.5.3 Microwave Extraction Microwave Assisted Hydrodistillation Theory of Microwave Principle of MAHD Extraction Mechanism of Microwave Assisted Hydrodistillation Heat Transfer in Microwave Assisted Hydrodistillation Types of MAHD Effects of Operating Factors on Efficiency of MAHD Nature and Volume of Solvent Extraction Time Microwave Irradiation Power or Temperature Characterization of Essential Oil Gas Chromatography-Mass Spectrometry (GC-MS) Scanning Electron Microscopy (SEM) Fourier Transform Infrared Spectroscopy (FTIR) Bioassay Growth of Artemia Salina Statistical Model Factorial Design Central Composite Design Summary 55 CHAPTER 3 MATERIALS AND METHODS 3.1 Introduction Materials Raw Material Chemicals 3.3 Methods Preparation of Raw Material Extraction of Cinnamomum cassia Bark Oil through Microwave Assisted Hydrodistillation (MAHD) Extraction of Cinnamomum cassia Bark Oil through Hydrodistillation (HD vii

8 3.4 Optimization of Cassia Bark Oil Extraction One Factor at a Time (OFAT) Screening of MAHD Extraction Parameters using Factorial Design Optimization of MAHD Extraction Parameters using Response Surface Methodology (RSM) 3.5 Analysis Calculation of Extracted Cassia Oil Yield Gas Chromatography-Mass Spectrometry (GS-MS) Fourier Transform Infrared Spectroscopy (FTIR) Scanning Electron Microscopy (SEM) Analysis 3.6 Brine Shrimp Lethality Bioassay Brine Shrimp Hatching Sample Preparation Brine Shrimp Bioassay 3.7 Temperature Analysis CHAPTER 4 RESULTS AND DISCUSSION 4.1 Preliminary Study Selection of Factor Range Pre-Extraction Processes 4.2 Effects of Operating Parameters Effect of Water-to-Cinnamon Powder Ratio on Yield Effect of Extraction Period on Yield Effect of Irradiation Power on Yield and Induction Time 4.3 Optimization of MAHD Parameters Factorial Analysis of MAHD Parameters Optimization of Cinnamon Bark Oil Extraction through MAHD by using Response Surface Method Fit Summary and Analysis of Variance (ANOVA) Effect of Independent Processing Parameters Effect of Interactive Factors Model Validation viii

9 4.3.7 Comparison between OFAT Method and Response Surface 103 Method Effects on Yield of Cinnamon Bark Oil 4.4 Morphological Studies of Cinnamon Powder Surface Morphology of Untreated and Pre-treated Cinnamon Bark Powder Morphological Changes to Cinnamon Bark After Extraction with MAHD and HD 4.5 Spectra Analysis of Essential Oil Cinnamon Bark Oil Identification of Cinnamon Bark Oil Crude Extract Classification of Cinnamon Bark Oil Crude Extract 4.7 Heat Generation System and Dielectric Properties of MAHD Extraction Introduction Temperature Analysis Volumetric Rate of Heat Generation Dielectric Properties Penetration Depth 4.8 Cytotoxicity Bioassay Cytotoxicity of Cinnamon Bark Oil Energy, Economy and Environmental Impact CHAPTER 5 CONCLUSION AND RECOMMENDATIONS 7.1 Conclusion Recommendations 144 REFERENCES APPENDICES LIST OF PUBLICATIONS ix

10 LIST OF TABLES Table No. Title Page 2.1 Comparison among advance extraction techniques Dielectric properties of commonly used solvents in extraction Major microwave parts and functions Functions of equipment used for essential oil analysis Some examples of infrared absorption frequencies Summary of brine shrimp lethality test on Cinnamomum species List of chemicals Overall parameters and conditions of MAHD extraction process 3.3 Overall parameters and conditions of HD extraction process 3.4 Two level factorial design experiment matrix with response variable Design Summary Experimental design plan and responses Test of Significant for the extracted cinnamon bark oil Results for the test goodness of fit Experimental layout of Central Composite Design (CCD) in extraction of cinnamon bark oil yield ANOVA for response surface quadratic model Validation results Summary of functional groups present in cinnamon bark oil obtained through HD and MAHD 110 x

11 Table No. Title Page 4.7 Relative content (%) of chemical components present in crude extract of cinnamon bark oil extracted through MAHD and HD for various extraction time 4.8 Mean chemical compositions (%) of the crude extract of cinnamon bark oil extracted through MAHD and HD at optimum conditions 4.9 LC50 values of cinnamon bark oil crude extracts against A. salina 4.10 Summary of energy consumption and CO2 emission of MAHD and HD methods xi

12 LIST OF FIGURES Figures No. Title Page 2.1 Chemical structure of trans-cinnamaldehyde Setup for microwave dry-diffusion and gravity process Setup for microwave steam distillation (MSD) Schematic diagram of principle of microwave steam Diffusion (MSDf). 2.5 Scanning electron micrographs of orange peel (a) untreated, (b) after MAD for 30 min and (c) after HD for 3h 2.6 Scanning electron micrographs of thyme leaves for (a) untreated (b) after HD (60 min) and (c) after MAHD (30 min) 2.7 Fundamental mechanism of mass and heat transfer in conventional microwave extraction Life cycle of Artemia salina brine shrimp Flow process of the general experimental procedure Fresh Cinnamomum cassia (cinnamon) barks Illustration of C. cassia bark sample preparation Modified domestic microwave oven with Pico TC-08-USB data collector 4.1 Effect of different water-to-raw material ratio on extraction yield of MAHD and HD at fixed irradiation power of 225 W and extraction time of 90 min 4.2 Effect of different extraction time on yield of cinnamon bark oil by MAHD and HD at fixed irradiation power of 225 W and water to cinnamon powder ratio of 8:1 4.3 Effect of various irradiation power on cinnamon bark oil yield (%) and induction time (min) of MAHD and HD at fixed extraction time of 90 min and water-to-cinnamon powder ratio of 8: xii

13 Figures No. Title Page 4.4 Effect of extraction methods on cinnamon bark oil yield (%) and induction time (min) of MAHD (225 W) and HD (350 W) at fixed extraction time of 90 min and water-to-cinnamon powder ratio of 8:1 4.5 Pareto s chart of standardize effects of factors using the cinnamon bark oil yield (A: Water: raw material ratio, B: Microwave power, C: Extraction time) 4.6 Response surface plot of extracted cinnamon bark oil yield as a function of: (a) water: raw material ratio (A) and microwave power (B) at fixed extraction time of 75 min; (b) water: raw material ratio and extraction time (C) fixed microwave power of 225W; (c) microwave power and extraction time at fixed water: raw material ratio of 8:1 4.7 Comparison on response of the yield of predicted and experimental cinnamon bark oil 4.8 Effect of various irradiation power on cinnamon bark oil yield (%) and induction time (min) of MAHD and HD at fixed extraction time of 90 min and water-to-cinnamon 4.9 Effect of independent factors: (a) microwave power (W), (b) water: raw material ratio (w/w) and (c) extraction time (min) on the yield of cinnamon bark oil 4.10 Response surface of cinnamon bark oil yield as function of (a) microwave power and water: cinnamon powder ratio at extraction time of 75 min, (b) microwave power and extraction time at water: cinnamon powder ratio of 8:1 and (c) water: raw material ratio and extraction time at microwave power of 225 W 4.11 Contour plot of cinnamon bark oil yield as function of (a) microwave power and water: cinnamon powder ratio at extraction time of 75 min, (b) microwave power and extraction time at water: cinnamon powder ratio of 8:1 and (c) water: raw material ratio and extraction time at microwave power of 225 W 4.12 SEM images of (a) untreated raw cinnamon bark powder and (b) pre-treated cinamon bark powder after soaking for 30 min xiii

14 Figures No. Title Page 4.13 Scanning electron micrographs of oil cell glands of cinnamon bark (a) after pre-treatment (soaking for 30 min), (b) after MAHD extraction (75 min) and (c) after HD extraction (150 min) 4.14 FTIR spectra of cinnamon bark oil obtained through MAHD and HD 4.15 GC-MS chromatogram of MAHD at 30 min extraction time at fixed water: cinnamon powder ratio of 8:1 and microwave power of 225 W 4.16 GC-MS chromatogram of HD at 30 min extraction time at fixed water: cinnamon powder ratio of 8:1 and constant operating power supply of 350 W 4.17 Composition of chemical classes at various extraction time obtained through MAHD 4.18 Composition of chemical classes at various extraction time obtained through HD 4.19 Temperature profile of cinnamon matrix extracted through MAHD at water: cinnamon powder ratio of 8:1 and microwave power of 225 W 4.20 Rate of temperature increase profile of cinnamon matrix extracted through MAHD at water: cinnamon powder ratio of 8:1 and microwave power level of 225 W 4.21 Volume rate of heat generation of cinnamon matrix extracted through MAHD at water: cinnamon powder ratio of 8:1 and microwave power level of 225 W for various microwave irradiation time 4.22 Dielectric constant (ε') at various temperature of cinnamon bark matrix extracted through MAHD at 225 W of irradiation power and 8:1 ratio of water to cinnamon bark powder 4.23 Dielectric loss (ε'') at different temperature of cinnamon bark matrix extracted through MAHD at 225 W of irradiation power and 8:1 ratio of water to cinnamon bark powder 4.24 Penetration depth, Dp, at various temperature of cinnamon bark matrix extracted through MAHD at 225 W of irradiation power and 8:1 ratio of water to cinnamon bark powder xiv

15 Figures No. Title Page 4.25 Probit graph for MAHD Probit graph for HD Probit graph for K2Cr7O2 140 xv

16 LIST OF SYMBOLS tan δ Dielectric loss tangent ε Dielectric constant ε'' E P f Dielectric loss Electric field strength Microwave power distribution per volume unit Frequency Volume of heat generation ρ Density Heat capacity Փ T Volume fraction Temperature (⁰C) Penetration depth λ Wavelength µm Micrometer +α Positive axial -α Negative axial Number of interactions xvi

17 LIST OF ABBREVATIONS AACC ANOVA BBD BLT CAMD CCD DCM DMSO EM FMASE FTIR GC-MS GRAS HD MAE MAHD MASD MDG MHG MSD MSDf NIST OFAT American Association of Cereal Chemists Analysis of Variance Box-Behken Design Brine Shrimp Lethality Test Compressed Air Microwave Distillation Central Composite Design Dichloromethane Dimethyl Sulfoxide Electromagnetic Focused Microwave Assisted Soxhlet or Solvent Extraction Fourier Transform Infrared Spectroscopy Gas Chromatography-Mass Spectrometry Generally Response as Safe Hydrodistillation Microwave-Assisted Extraction Microwave Assisted Hydrodistillation Microwave Accelerated Steam Distillation Microwave Dry-Diffusion and Gravity Process Microwave Hydrodiffusion and Gravity Microwave Steam Distillation Microwave Steam Diffusion National Institute of Standards and Technology One Factor at a Time xvii

18 PMAE PTFE RSM RT SEM SFE SFME TDS UAE VMHD Portable Microwave Assisted Extraction Polytetraflouro Ethylene Response Surface Methodology Retention Time Scanning Electron Microscopy Supercritical Fluid Extraction Solvent Free Microwave Extraction Triple Distribution System Ultrasound Assisted Extraction Vacuum Microwave Hydrodistillation xviii

19 LIST OF APPENDICES Appendix No. Title Page A1 A2 A3 A4 A5 A6 A7 A8 B1 B2 B3 GC-MS chromatogram of MAHD at 60 min extraction time at fixed water: cinnamon powder ratio of 8:1 and microwave power level of 225 W GC-MS chromatogram of MAHD at 90 min extraction time at fixed water: cinnamon powder ratio of 8:1 and microwave power level of 225 W GC-MS chromatogram of MAHD at 120 min extraction time at fixed water: cinnamon powder ratio of 8:1 and microwave power level of 225 W GC-MS chromatogram of HD at 60 min extraction time at fixed water: cinnamon powder ratio of 8:1 and constant power supply of 350 W GC-MS chromatogram of HD at 90 min extraction time at fixed water: cinnamon powder ratio of 8:1 and constant power supply of 350 W GC-MS chromatogram of HD at 120 min extraction time at fixed water: cinnamon powder ratio of 8:1 and constant power supply of 350 W GC-MS chromatogram of HD at 150 min extraction time at fixed water: cinnamon powder ratio of 8:1 and constant power supply of 350 W GC-MS chromatogram of HD at 180 min extraction time at fixed water: cinnamon powder ratio of 8:1 and constant power supply of 350 W Temperature profile of cinnamon matrix extracted through MAHD at water: cinnamon powder ratio of 8:1 and microwave power of 200 W Rate of temperature increase profile of cinnamon matrix extracted through MAHD at water: cinnamon powder ratio of 8:1 and microwave power of 200 W Temperature profile of cinnamon matrix extracted through MAHD at water: cinnamon powder ratio of 8:1 and microwave power of 250 W xix

20 Appendix No. Title Page B4 B5 B6 B7 C1 C2 Rate of temperature increase profile of cinnamon matrix extracted through MAHD at water: cinnamon powder ratio of 8:1 and microwave power of 250 W Calculations of volume rate of heat generation, Q at 225 W of microwave power and 8:1 of water-to-cinnamon powder ratio Calculations of dielectric constant and dielectric loss of mixture, at 225 W of microwave power and 8:1 of waterto-cinnamon powder ratio Calculations of penetration depth at 225 W of microwave power and 8:1 of water-to-cinnamon powder ratio Calculation on energy consumption and emission of carbon dioxide for MAHD Calculation on energy consumption and emission of carbon dioxide for HD xx