Prepare the indigestible dextrin from rice starch by pyrolysis with different catalysts and characterise their product

MINISTRY OF EDUCATION AND TRAINING NHA TRANG UNIVERSITY MAI VU HOANG GIANG PREPARE THE INDIGESTIBLE DEXTRIN FROM RICE STARCH BY PYROLYSIS WITH DIFFERENT CATALYSTS AND CHARACTERISE THEIR PRODUCT MASTER THESIS KHANH HOA - 2020 MINISTRY OF EDUCATION AND TRAINING NHA TRANG UNIVERSITY Ơ MAI VU HOANG GIANG PREPARE THE INDIGESTIBLE DEXTRIN FROM RICE STARCH BY PYROLYSIS WITH DIFFERENT CATALYSTS AND CHARACTERISE THEIR PRODUCT MASTER THESIS Major Food of technology 192/QĐ-ĐHNT Topic allocation Decision Decision on establing the commitee: Defense date: 19/09/2020 Suppervisor: Assoc.Prof.Dr Nguyen Duy Lam Chairman: Dr Khong Trung Thang Faculty of Graduate Studies: KHANH HOA - 2020 UNDERTAKING I undertake that the thesis entitled ―Prepare the indigestible dextrin from rice starch by pyrolysis with different catalysts and characterise their product‖ is my own work The work has not been presented elsewhere for assessment until the time this thesis is submitted Ha Noi, Date month year 2020 Author Mai Vu Hoang Giang iii ACKNOWLEDGMENT I would like to express my deepest appreciation to the teachers in the Food Technology Faculty of Nha Trang University (NTU) for helping and offering the best conditions for me to complete the thesis My special thanks go to Assoc Prof Dr Nguyen Duy Lam for the continuous support of my master study and research, for his patience, motivation, enthusiasm, and immense knowledge His guidance helped me in all the time of research and writing of this thesis I would like to express my sincere gratitude to many researchers and staff of the Center of Food Quality and Safety Research (CEFORES) under the Vietnam Institute of Agricultural Engineering and Post-harvest Technology (VIAEP) for supporting and facilitating me during the time of researching and doing the thesis Last but not the least, I would like to thank my parents and to my brothers and sister for supporting me spiritually throughout writing this thesis Thank you! Ha Noi, Date month year 2020 Author Mai Vu Hoang Giang iv TABLE OF CONTENT UNDERTAKING iii ACKNOWLEDGMENT iv TABLE OF CONTENT v LIST OF ABBREVIATIONS ix LIST OF TABLES x LIST OF FIGURES xi ABSTRACT xiv CHAPTER INTRODUCTION 1.1 Introduction 1.2 Research objectives 1.2.1 Main objective 1.2.2 Specific objectives CHAPTER OVERVIEW OF RESEARCH ISSUES 2.1 Introduction of resistant dextrin 2.1.1 Starch, rice starch and modified starch 2.1.2 Resistant starch 2.1.3 Resistant dextrin 2.1.4 Biological activity, health significance and food additive 2.1.5 Resistant dextrin/maltodextrin market 10 2.2 Starch pyrolysis to create pyrodextrin with acid catalyst .10 2.2.1 Steps of starch pyrolysis with acid catalyst 10 2.2.2 Pyrolysis reactions and the formation of indigestible fraction 12 2.3 Starch pyrolysis to create pyrodextrin with gamma radiation as catalyst 14 2.3.1 The effect of gamma irradiation on starch 14 2.3.2 The effect of irradiation treatment on the content of resistant starch 15 2.4 Starch pyrolysis to create pyrodextrin with other catalysts 16 v 2.5 Characteristics of resistant pyrodextrin and typical analytical techniques 17 2.5.1 Characteristics of resistant dextrin 17 2.5.2 Typical analytical methods 18 CHAPTER MATERIALS AND METHODS OF RESEARCH 20 3.1 Research subjects 20 3.2 Chemicals .20 3.2.1 Kit sets 20 3.2.2 Acids used as catalysts 20 3.2.3 Other analytical chemicals 20 3.3 Equipment and tools 21 3.4 Experiment design 21 3.4.1 Experiment Effects of different acid on pyrolysis 21 3.4.2 Experiment Effect of concentration of HCl on pyrolysis .22 3.4.3 Experiment Effect of pyrolysis temperature 22 3.4.4 Experiment Effect of pyrolysis time .22 3.4.5 Experiment Effects of gamma radiation in different doses 23 3.4.6 Experiment Effect of gamma radiation in different dose rates .23 3.4.7 Experiment Effect of gamma irradiation combined with non-acidic catalysist pyrolysis 23 3.4.8 Experiment Effect of gamma irradiation combined with HCl catalysist pyrolysis 24 3.4.9 Experiment Effect of the rate of activated carbon added 24 3.4.10 Experiment 10 Effect of pyrolysis time with activated carbon catalyst 24 3.4.11 Experiment 11 Verification of pyrolysis at pilot scale and final product charactification .24 3.5 Analytical methods 25 3.5.1 Indigestible Fraction (IDF) 25 3.5.2 Total Dieatary Fiber (TDF) 25 3.5.3 Color difference 25 3.5.4 Water absorption 26 3.5.5 Solubility .26 vi 3.5.6 pH of starch and dextrin 27 3.5.7 Protein and crude fat content 27 3.5.8 Investigation with scanning electron microscope (SEM) 27 3.5.9 Investigation by X-ray diffraction measurement (XRD) 28 3.5.10 Fourier transform infrared spectrometry (FTIR) .28 3.5.11 Differential scanning calorimetry (DSC/DTA) .28 3.5.12 Rapid viscosity analysis (RVA) 28 CHAPTER RESULTS AND DISCUSSION 30 4.1 Acid catalytic effect on pyrolysis to create resistant dextrin from rice starch .30 4.1.1 Effect of some acid as catalyst on products of pyrolysis 30 4.1.2 Effect of concentration of HCl as catalyst on products of pyrolysis 33 4.1.3 Effect of pyrolysis temperature on products of reaction 35 4.1.4 Effect of pyrolysis time on products of reaction 37 4.2 Effects of gamma-ray radiation on rice starch .40 4.2.1 Effect of gamma-ray radiation on the indigestible fraction 40 4.2.2 Effect of radiation dose rate on the indigestible fraction 42 4.2.3 Effects of gamma-ray radiation on physicochemical properties 43 4.2.4 Effects of gamma-ray radiation on molercular structure 48 4.3 The gamma-ray radiation as catalysits for pyrolysis to create indigestible dextrin from rice starch 53 4.3.1 Change in the indigestible fraction 53 4.3.2 Change in the whiteness of dextrin 54 4.3.3 Change in the solubility and pH of dextrin 55 4.3.4 Change in molercular structue .56 4.4 The effect of gamma-ray radiation combined with acid catalyst on pyrolysis to create resistance dextrin from rice starch 60 4.4.1 Pyrolysis having the same duration 60 4.4.2 Pyrolysis having whiteness 65% 61 4.4.3 Pyrolysis at different temperatures to the same 65% whiteness 63 4.4.4 Change in molercular structure 64 vii 4.5 The effects of gamma-ray radiation, acid and activated carbon on pyrolysis create pyrodextrin from rice starch 66 4.5.1 The effect of activated carbon with different rate added 66 4.5.2 Effect of activated carbon with different pyrolysis duration .69 4.6 Technological flowchart and its verification at pilot scale 72 4.6.1 Process flowchart and process description 72 4.6.2 Quality parameters of final product 76 CHAPTER CONCLUSION AND RECOMMENDATION .78 5.1 Conclusion 78 5.2 Recommendation 78 REFRENCES .79 APPENDIX 1: Some other analytical methods I APPENDIX 2: Results of data processing on Minitab VII APPENDIX 3: Pictures of some laboratory equipment and tools XXVIII APPENDIX 4: Pictures of some experiments and products XXXI APPENDIX Spectrums of XRD, FTIR, DSC/TGA, SEM, RVA XXXIV viii LIST OF ABBREVIATIONS AACC : American Association for Clinical Chemistry AOAC : Association of Official Analytical Chemists DE : Dextrose Equivalent DF : Dietary Fiber DP : Degree of Polymerization DP : Degrees of polymerization DTA : Differentail thermal analysis EPR : Electron paramagnetic resonance FAO : Food and Agriculture Organization of the United Nations FDA : Food and Drug Administration GMP : Good Manufacturing Practices GPC : Gel permeation chromatography GRAS : Generally Recognized as Safe IDF : Indigestible Dextrin Fraction MS : Mass spectrometry RMD : Resistance Maltodextrin rpm : Rotation per minute RS : Rice starch RVA : Rapid visco analyser STMP : Sodium trimetaphosphate STPP : Sodium tripolyphosphate TCVN : Vietnam Standard TGA : Thermogravimetric analysis WHO : World Health Organization ix LIST OF TABLES Table 4.1 Effect of acid concentration on quality of resistant dextrin products 34 Table 4.2 Change in RVA viscosity characteristics of irradiated starch 47 Table 4.3 The weight reduction of specific samples 51 Table 4.4 The quality of final product 76 Table 4.5 The weight reduction of specific samples 76 x in roasting equipment with capacity of kg/batch XXX APPENDIX 4: Pictures of some experiments and products Dry starch to 4-5% moisture by Memmert dryer Dry starch to 4-5% moisture by in roasting equipment with capacity of kg/batch XXXI Mixing starch with acid HCl by spray machine Actived carbon supplement XXXII Starch containers for irradiation with dosimeters Visual color of starch after pyrolysis with acid and actived carbon catalysists at 8kg scale pilot XXXIII APPENDIX Spectrums of XRD, FTIR, DSC/TGA, SEM, RVA A B C D A : TG result of starch at kGy B : TG result of starch at 10 kGy C : TG result of starch at 30 kGy XXXIV D : TG result of starch at 50 kGy E F G H E : TG result of starch at kGy F : TG result of starch at 10 kGy G : TG result of starch at 30 kGy H : TG result of starch at 50 kGy XXXV CX10-PN PDF 00-055-1799 ( C6 H10 O5 )n Starch (maize) CX0-PN PDF 00-055-1799 ( C6 H10 O5 )n Starch (maize) 4000 4000 3000 Counts Counts 3000 2000 2000 1000 1000 0 10 20 30 40 50 10 60 20 30 40 50 60 2Theta (Coupled TwoTheta/Theta) WL=1.54060 2Theta (Coupled TwoTheta/Theta) WL=1.54060 CX50-PN PDF 00-055-1799 ( C6 H10 O5 )n Starch (maize) CX30-PN PDF 00-055-1799 ( C6 H10 O5 )n Starch (maize) 4000 4000 3000 Counts Counts 3000 2000 2000 1000 1000 0 10 20 30 40 50 60 10 2Theta (Coupled TwoTheta/Theta) WL=1.54060 20 30 40 50 2Theta (Coupled TwoTheta/Theta) WL=1.54060 1: XRD result of starch at 0kGy with pyrolysis 2: XRD result of starch at 10kGy with pyrolysis 3: XRD result of starch at 30kGy with pyrolysis 4: XRD result of starch at 50kGy with pyrolysi XXXVI 60 CX10-HCl-PN PDF 00-055-1798 ( C6 H10 O5 )n Starch (maize) CX0-HCl-PN PDF 00-055-1798 ( C6 H10 O5 )n Starch (maize) 4000 4000 3000 Counts Counts 3000 2000 2000 1000 1000 0 10 20 30 40 50 10 60 20 30 40 50 60 2Theta (Coupled TwoTheta/Theta) WL=1.54060 2Theta (Coupled TwoTheta/Theta) WL=1.54060 CX30-HCl-PN PDF 00-055-1798 ( C6 H10 O5 )n Starch (maize) CX5O-HCl-PN PDF 00-055-1798 ( C6 H10 O5 )n Starch (maize) 4000 4000 3000 Counts Counts 3000 2000 2000 1000 1000 0 10 10 20 30 40 50 20 30 40 60 2Theta (Coupled TwoTheta/Theta) WL=1.54060 2Theta (Coupled TwoTheta/Theta) WL=1.54060 5: XRD result of starch irradiated combined acid catalyst for pyrolysis at kGy 6: XRD result of starch irradiated combined acid catalyst for pyrolysis at 10 kGy 7: XRD result of starch irradiated combined acid catalyst for pyrolysis at 30 kGy 8: 7: XRD result of starch irradiated combined acid catalyst for pyrolysis at 50 kGy XXXVII 50 60 58 Cx10NP Cx0NP 74 56 72 70 50 54 B1 44 575.96 46 1079.92 A1 56 %Transmittance 58 1152.80 48 1152.93 60 1079.64 42 1024.28 52 50 40 1025.66 %Transmittance 62 52 2930.44 64 1379.79 1636.97 2931.23 66 1640.18 1381.95 54 68 38 48 46 36 44 34 42 4000 3500 3000 2500 2000 Wavenumbers (cm-1) 1500 1000 4000 500 Cx30NP 3500 3000 2500 2000 Wavenumbers (cm-1) 1500 1000 500 1000 500 75 Cx50NP 74 82 73 80 68 67 66 68 1152.76 C1 66 64 60 64 D1 63 62 61 60 1079.22 62 65 1152.39 %Transmittance 70 59 409.03 56 57 56 55 54 52 4000 406.60 58 58 1024.67 %Transmittance 72 1418.90 69 1379.74 2930.16 74 1638.70 70 1637.07 71 76 2929.52 72 78 3500 3000 2500 2000 Wavenumbers (cm-1) 1500 1000 54 53 500 4000 A1 : FTIR result of starch irradiated and pyrolysis at kGy B1 : FTIR result of starch irradiated and pyrolysis at 10 kGy XXXVIII 3500 3000 2500 2000 Wavenumbers (cm-1) 1500 C1 : FTIR result of starch irradiated and pyrolysis at 30 kGy D1 : FTIR result of starch irradiated and pyrolysis at 50 kGy 88 Cx0NPHCl 88 Cx10NPHCl 86 86 84 1150.86 70 F1 68 66 1078.25 E1 74 1152.77 72 %Transmittance %Transmittance 76 578.94 74 1383.91 78 76 78 1638.93 577.31 80 2932.18 80 1419.36 1633.11 2927.93 82 762.54 82 84 64 72 62 70 1027.25 60 58 1024.63 68 56 66 54 52 64 50 62 48 4000 3500 3000 2500 2000 Wavenumbers (cm-1) 1500 1000 4000 500 3500 3000 2500 2000 Wavenumbers (cm-1) 1500 1000 500 84 Cx50NPHCl 72 Cx30NPHCL 70 82 68 80 66 64 78 62 1152.57 44 575.96 46 42 40 70 H1 68 66 1151.98 G1 48 1381.64 72 52 50 1634.55 925.97 74 64 62 38 36 60 1078.28 34 58 32 407.28 %Transmittance 54 %Transmittance 56 76 2929.64 2929.80 58 1383.84 1639.66 60 56 30 28 54 26 52 24 4000 3500 3000 2500 2000 Wavenumbers (cm-1) 1500 1000 500 4000 3500 E1 : FTIR result of starch irradiated and pyrolysis at kGy with acid catalyst F1 : FTIR result of starch irradiated and pyrolysis at 10 kGy with acid catalyst G1 : FTIR result of starch irradiated and pyrolysis at 30 kGy with acid catalyst H1 : FTIR result of starch irradiated and pyrolysis at 50 kGy with acid catalyst XXXIX 3000 2500 2000 Wavenumbers (cm-1) 1500 1000 500 MINISTRY OF EDUCATION & TRAINING NHA TRANG UNIVERSITY SOCIALIST REPUBLIC OF VIETNAM Independence - Freedom - Happiness REPORT OF THESIS CORRECTION At the request of the thesis evaluation Committee Full name: Mai Vu Hoang Giang Student code: 60DT41 Thesis title: “PREPARE THE INDIGESTIBLE DEXTRIN FROM RICE STARCH BY PYROLYSIS WITH DIFFERENT CATALYSTS AND CHARACTERISE THEIR PRODUCT” Supervisor : Assoc.Prof.Dr Nguyen Duy Lam Study Program : Master Food of technology Thesis defense date : 19/9/2020 Based on the requirements of thesis evaluation committee I would like submit the revised thesis statement as follows: Request 1: Correct the spelling and grammar Content has been modified: For example: Clohydric hydrochloric Acid citric citric acid Acid lactic lactic acid ………… Request 2: Correct the format of thesis Content has been modified: For example: Correct the format all of table Correct the format in title of figure ……… Request 3: Correct the title of thesis: Prepare preparation Characterise characterisation Content has been modified: We would like to accept the committee's opinion on this matter, but since a decision has been made on this topic, we would like to keep the title Request 4: Correct the content of thesis: Content has been modified: For example: Add a method of determining the whiteness Add some the results and discussion, for example: the discussion on figure 4.36, 4.37,… Nha Trang, date 20 month year 2020 Student (sign and full name) Mai Vu Hoang Giang Chairman (sign and full name) Supervisor (sign and full name) Nguyen Duy Lam MINISTRY OF EDUCATION & TRAINING NHA TRANG UNIVERSITY SOCIALIST REPUBLIC OF VIETNAM Independence - Freedom - Happiness REPORT OF ANSWERING THE QUESTIONS Of the thesis evaluation Committee Full name:Mai Vu Hoang Giang Student code: 60DT41 Thesis title: “PREPARE THE INDIGESTIBLE DEXTRIN FROM RICE STARCH BY PYROLYSIS WITH DIFFERENT CATALYSTS AND CHARACTERISE THEIR PRODUCT” Supervisor : Assoc.Prof.Dr Nguyen Duy Lam Study Program : Master Food of technology Thesis defense date : 19/9/2020 CONTENT: Question 1: Why did you choose SEM, XRD, FTIR for characterization of the product? Answer: SEM indicate the morphological changes, some foreign studies have shown that starch morphology changes at high irradiated doses and is affected by heat XRD and FTIR indicate the structural change if any These analysis criteria have become popular and classic in starch research So we chose it Question 2: How you know that the rice starch converts to dextrin? How much the yield? Answer: Based on the solubility of starch in water Starch is usually insoluble in water, but gelatinized if heated to 70-80C, and dextrin is dissolved Completely convert when completely dissolved in warm water into a clear solution Metabolic yield may be based on solubility Question 3: Why did viscosities of irradiated starch decrease with irradiation treatment for a long time? Answer: Gamma radiation is ionizing radiation, due to the amylose chain break effect at 1-4 bonds, it reduces the molecular mass The mechanism is somewhat similar to the enzyme alpha amylase, i.e random cut of glycozidic bonds The viscosity of starch or other biopolymers is inversely proportional to the molecular weight, so it is less than irradiation with high dose, long time Question 4: Why did you use gamma-irradiation instead of other rays: UV-Vis,… What the mechanism behind the pyrolysis of rice starch using acid catalyst ;gamma radiation in the presence of acid? Answer: Gamma radiation has high energy, high depth of penetration, while UV only has effect on material surface The mechanism of pyrolysis with acid catalysis is pyrolysis, in which the role of the acid is to weaken the bonds and partially hydrolyze the acid When pyrolysis, it is easy to take place hydrolysis and cross-linking, forming bonds that are not broken by digestive enzymes The role of irradiation similar acid Question 5: What is the role of actived carbon? Answer: The actived carbon as a catalyst to be able to decolorize dextrin Question 6: What are the desired value of whiteness, IDF, solubility of commercial resistant dextrin? Recommend the factor ( acid concentration, irradiation time, dose, actived carbon) to obtain the desired values Answer: It is desirable to create products with the highest whiteness, IDF, solubility (100%), but these quality indicators are mostly inversely proportional to each other, for example whiteness with IDF should be chosen appropriate and possibly optimized Suggested factors are: acid concentration, irradiation dose, temperature and time pyrolysis Question 7: Did you compare your product with commercial product aboout price, quality? Answer: No, the reason is that the dissertation's results are only part of the state-level topic that students participate in The topic has not ended, so the price cannot be calculated In terms of quality, it was compared with commercial products, but the results were not agreed upon in the thesis However, it is known that the quality of the research product is not inferior to that produced by foreign countries Question 8: Are there any comparism between the synthesized resistant starch and the commerical one? Answer: The answer has been mentioned in the answer of question Question 9: Could you explain the results of Figure 4.32? Why did the irradiated starch at 50 kGy has the indigestible fraction decrease? Answer: There is no decrease of indigestible fraction at 50 kGy irradiation dose In fact, the indigestible fraction of dextrin at 40 and 50 kGy did not increase There is no difference between the indigestuble fraction of dextrin at 40 and 50 kGy (p