Nghiên cứu quá trình tinh chế cinnamaldehyde từ tinh dầu quế bằng hệ thống chưng luyện tiên tiến

HANOI UNIVERSITY OF SCIENCE AND TECHNOLOGY MASTER THESIS Study on the process of purifying cinnamaldehyde from cinnamon cassia oil by using an advanced distillation method PHAN NGOC QUANG Quang.PN202763M@sis.hust.edu.vn Chemical Engineering Supervisor: Dr Nguyen Trung Dung School of Chemical Engineering Signature of supervisor Hanoi, 08/2022 TRƯỜNG ĐẠI HỌC BÁCH KHOA HÀ NỘI LUẬN VĂN THẠC SĨ Nghiên cứu trình tinh chế Cinnamaldehyde từ tinh dầu quế hệ thống chưng luyện tiên tiến PHAN NGỌC QUANG Quang.PN202763M@sis.hust.edu.vn Ngành: Kỹ thuật Hóa học Giảng viên hướng dẫn: TS Nguyễn Trung Dũng Viện: Kỹ thuật Hóa học Hà Nội, 08/2022 CỘNG HÒA XÃ HỘI CHỦ NGHĨA VIỆT NAM Độc lập – Tự – Hạnh phúc BẢN XÁC NHẬN CHỈNH SỬA LUẬN VĂN THẠC SĨ Họ tên tác giả luận văn: PHAN NGỌC QUANG Đề tài luận văn : Nghiên cứu trình tinh chế Cinnamaldehyde từ tinh dầu quế hệ thống chưng luyện tiên tiến Chuyên ngành: Kỹ thuật hóa học Số hiệu học viên: 20202763M Tác giả, người hướng dẫn khoa học Hội đồng chấm luận văn xác nhận tác giả sửa chữa, bổ sung luận văn theo biên họp Hội đồng ngày 27/08/2022 với nội dung sau: - Bổ sung kết nghiên cứu có Việt Nam giới phần tổng quan Bổ sung phần hồi lưu Hình 3.4 Thay tỷ số QB/F QB/P phần 3.5 Ngày Giảng viên hướng dẫn tháng năm Tác giả luận văn CHỦ TỊCH HỘI ĐỒNG ĐỀ TÀI LUẬN VĂN Nghiên cứu trình tinh chế Cinnamaldehyde từ tinh dầu quế hệ thống chưng luyện tiên tiến Giảng viên hướng dẫn Ký ghi rõ họ tên ACKNOWLEDGEMENT First of all, I really appreciate my family that is my biggest motivation, for giving me the best to study and practice so far Secondly, I would like to express my deep appreciation to my supervisor Dr Nguyen Trung Dung, for pursuing my Master’s study at the School of Chemical Engineering, Hanoi University of Science and Technology, giving me a great chance to intern at the National Polytechnic Institute of Toulouse and many precious contributions to complete this thesis Because of my thesis defense, he had to delay his work One more time I really appreciate him I also would like to give precious thanks to Dr Ta Hong Duc, who is a crucial person in my career path He always believed, motivated, directed, and gave me many great opportunities to achieve my expectations Besides, he encouraged me to take part in related programs, seminars, and outside programs to improve my horizon One more time, I really appreciate his help on my path I also really appreciate Dr Cao Hong Ha, who helped directly me a lot from first technics to making experiments and scientific ideas for my research from the first days when I began to approach the topic of my research in the laboratory Especially, I am really grateful for his perfect suggestions which help me improve significantly my knowledge a lot One more time, I would like to sincerely thank his help during all of my working time in the laboratory No matter where I go or anything in the future, I still want to be taught by him Besides that, I would like to thank Thầy Hiệp, who guided me in testing samples in my part-time job I would like to express my sincere thanks to Dr Phung Lan Huong, Assoc Prof Dr Chu Manh Hung, Assoc Prof Dr Nguyen Dac Trung, Assoc Prof Dr Dinh Van Hai, Ms Tran Vu Huong Tra, and Ms Trinh Thi Thuy Linh for not only giving me a valuable opportunity to study in France but also helping me wholeheartedly home country’s priority in the stressful time of the covid pandemic I would like to thank lecturers in the Department of Chemical Process Equipment for their teaching, giving me contributions, and always creating the best conditions for students to improve I also really appreciate Prof Michel Meyer, who gave me a perfect opportunity to work at LGC, INP-Toulouse, and supported me with great scientific ideas That is a duration of a memorable time in my life with Dr Benoit Mizzi who helped a lot in my work I would like to thank MSc Pham Duc Chinh always advised and supported me anytime In addition to being a lot of help came from my colleague Juan Bulle who is a good teammate We have a memorable duration of time when working together I really appreciate Mr Jean Louis Guy – “Thầy chủ nhà”, chị Linh, anh Bản, chị Ngân for their help during my working time in Toulouse I am really happy and lucky when I met them with a memorable time in Toulouse, France I also would like to warmly thank anh Nguyễn Chiêm Dương Thanh and my friends Trương Khánh Duyên, Lại Văn Duy, Bùi Văn Trường, Lê Công Tuấn who helped me in difficult time and other students in laboratory: Hảo, Mai, Ngọc, Thạch Mai – Máy hóa K62 and Cơng, Trọng – Hóa lý Last but not least, I would like to thank Prof Michel Meyer’s scholarship and Vallet scholarship 2021 and 2022 which are gratefully acknowledged A memorable journey closed to open the next journey with new interesting things Thanks and regards!!! SUMMARY The cinnamon tree is widely distributed throughout tropical and sub-tropical areas It is widely used as herbal medicine Vietnam is the world's third largest producer of cinnamon oil Cinnamon oil contains cinnamaldehyde (80-90%wt), eugenol, cinnamic acid, etc Therefore, it can be used to produce high purity Cinnamaldehyde (99%wt) via high-vacuum batch distillation (1–30mmHg) However, the disadvantages of the process are the relatively long separation time, the high energy consumption, and the loss of a large amount of Cinnamaldehyde into the light and middle cut-of components Two continuous columns were used to purify Cinnamaldehyde from Cinnamon cassia oil The NRTL thermodynamic model is used to calculate and simulate the process The preliminary configurations of columns were obtained by using the FUGK method, which is calculated by the DSTWU model in Aspen plus V10 The Radfrac model was used for the rigorous simulation The heat integration was performed when the vapor stream temperature in the second column was greater than the reboiler temperature in the first column by at least 10 oC The purity of Cinnamaldehyde was 0.99 mass fraction and the recovery ratio was 98.60% in all of the cases When P1=10mmHg, P2=20mmHg, heat integration was applied for process and QB,total,min =1326 cal/s Process intensification technology, which is one of the most significant advances in chemical engineering today, offers the potential for development in the chemical industry A divided wall column is an excellent illustration of a method for process intensification The optimal configurations of DWC are N 1=6, N2=14, N3=2, N4=6, N5=14, N6=7 with heat duty is 1219 cal/s at P=10mmHg Four different random packings (M-50, M-80, O-80, S-80) were characterized by HETP values when using mixture of n-Hexane and Cyclohexance at differrent concentrations The results showed that O-80 is the minimum HETP value in four type of packings Therefore, the applications of these packings in the industry are feasible CONTENTS ACKNOWLEDGEMENT ii SUMMARY iv LIST OF FIGURES iii LIST OF TABLES v LIST OF SYMBOLS AND ABBREVIATIONS vi INTRODUCTION CHAPTER LITERATURE REVIEW 1.1 Overview of Cinnamaldehyde 1.1.1 Introduction of Cinnamaldehyde 1.1.2 Application of Cinnamaldehyde 1.1.3 Preparation of Cinnamaldehyde 1.2 Overview of Cinnamon Cassia Oil 1.2.1 Origin and distribution in nature 1.2.2 Demand, production, benefits of using, and value of cinnamon cassia oil……………………………………………………………………… …… 1.3 Cinnamaldehyde purification technologies from Cinnamon Cassia Oil 10 1.3.1 Batch distillation model 10 1.3.2 Continuous distillation model 11 1.3.3 Divided wall column model 13 1.4 Conclusion chapter 19 CHAPTER METHOD OF STUDY 20 2.1 Determination of the thermodynamic model 20 2.2 Simulation method 20 2.2.1 Methodology of the continuous distillation column 20 2.2.2 Methodology of Divided wall column 21 2.3 Pinch technology 37 2.4 Method to evaluate the product quality 38 2.4.1 Determine the refractive index of the products 38 2.4.2 Gas Chromatography 39 i CHAPTER RESULTS AND DISCUSSION 40 3.1 Material characteristics 40 3.2 Choosing the best thermodynamic model 40 3.2.1 Experimental data 40 3.2.2 Simulation data 40 3.3 Continuous distillation 44 3.3.1 Shortcut calculation 44 3.3.2 Rigorous simulation 45 3.4 Divided wall column 52 3.4.1 Initial parameters for simulation 52 3.4.2 Sensibility analysis of Divided wall column 53 3.5 Comparison of three distillation models: batch column, continuous column and DWC 55 3.6 Determination of the HETP of the various random packing 56 3.6.1 Material of the packing 56 3.6.2 Distillation pilot plant 57 3.6.3 HETP calculation 59 CHAPTER CONCLUSION AND OUTLOOK 62 4.1 Conclusion 62 4.2 Outlook 62 APPENDIX 63 REFERENCES 67 ii LIST OF FIGURES Figure 1.1 Cinnamaldehyde Figure 1.2 Global Cinnamic Aldehyde Market, by the application (%) [1] .3 Figure 1.3 Crude cinnamon Cassia Oil .5 Figure 1.4 Cinnamon tree Figure 1.5 Supply of cinnamon oil Figure 1.6 Importers of cinnamon cassia oil Figure 1.7 Batch disstillation column 11 Figure 1.8 Conventional arrangements for separating three components mixture a)direct, b)indirect, c)sloppy sequences 14 Figure 1.9 Fully thermally coupled distillation column (Petlyuk column) 15 Figure 1.10 HIDiC disstilation column 15 Figure 1.11 Divided wall column 16 Figure 1.12 Seperation for ternary mixture in the divided wall column 16 Figure 1.13 Energy is lost separating the middle component B in the conventional arrangement 17 Figure 2.1 (a) DSTWU and (b) RADFRAC models in Aspen plus V10 21 Figure 2.2 Petlyuk column configuration 22 Figure 2.3 (a) Divided wall column; (b) Thermally coupled distillation .24 Figure 2.4 Simplified model design of divided wall column 25 Figure 2.5 The detailed structure and operating variables of a divided wall column 33 Figure 2.6 Types and position of dividing wall in the DWC system .35 Figure 2.7 A procedure for the design of a divided wall column 36 Figure 2.8 Schematic of pinch technology 37 Figure 2.9 Refraction of a light ray 38 Figure 2.10 Diagram of a gas chromatography 39 Figure 3.1 x,y-T diagram for the BA-CA system at 10kPa 41 Figure 3.2 x,y-T diagram for the BA-CA system at 20kPa 42 Figure 3.3 x,y-T diagram for the BA-CA system at 30k 43 Figure 3.4 Block flow diagram (BFD) of purification process 44 Figure 3.5 Plot of the relationship between P1, P2 and QB1, QB2, QB,total 47 Figure 3.6 Plot of TW1 and TD2 47 Figure 3.7 Graph of the relationship between P2-QB2 and comparison TW1-TD2 .49 Figure 3.8 Plot of TW1 at P1=10mmHg and TD2 at P2=15-100mmHg .49 Figure 3.9 Flowsheet of energy integration for two columns with case P1=10mmHg, P2=20mmHg 49 iii