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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 10oC 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 N1=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 .2 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 .2 Figure 1.2 Global Cinnamic Aldehyde Market, by the application (%) [1] .3 Figure 1.3 Crude cinnamon Cassia Oil 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 QB (cal/s) 2000 1800 1600 1400 Vertical position of the dividing wall 1200 Height of the dividing wall 1000 -8 -6 -4 -2 Figure 3.15 Effect of the height and vertical position of the wall on the heat duty of heat duty Secondly, the change in the heat duty of the reboiler is also analyzed and compared with the height of the dividing wall The height of the wall is 20 stages, as the shortcut result, marked zero in Figure 3.15 In the negative range, the number of stages of the dividing wall is decreased while in the positive range, the number of stages of the dividing wall is increased The feed and side product position remain the same as the initial parameters Figure 3.15 shows that the energy consumption of the divided wall column is lower if the number of stages decreases from 20 to 18 stages The heat duty of the reboiler is around 1298 cal/s The heat duty of the reboiler increased to 1410 cal/s when the height of the dividing wall increased to 22 stages Hence, the procedure for the design of divided wall columns gives structural parameters corresponding to the minimum energy demand of the column 3.4.2.2 Effect of the number of stages In the section, the change of the heat duty of the reboiler is studied when the number of stages of one section has changed while other sections are fixed as same as initial parameters The Figure 3.24 shows that the heat duty of the reboiler changes with the number of stages of each section In the negative range, the number of stages decreases and in the positive range, the number of stages increases 54 QB (cal/s) 2600 2400 2200 N1 N2 2000 N3 1800 N4 N5 1600 N6 1400 1200 1000 -4 -3 -2 -1 Figure 3.16 Effect of number of stages on heat duty of reboiler Figure 3.16 shows that the heat duty of the reboiler increases when the number of stages of each section decreases Theoretically, the numbers of stages decrease while remaining the specified product purity Hence, the reflux ratio has to increase Therefore, the heat duty of the reboiler will increase In Figure 3.16, the number of stages in sections 3, 5, and has a significant effect on the heat duty of the reboiler while the number of stages in sections 1,2, and are not affected significantly As the number of stages in each section increases, the heat duty of the reboiler slightly decreases as shown in Figure 3.16 Clearly, it is important to notice that the number of stages increases that means the capital cost of the system will increase 3.5 Comparison of three distillation models: batch column, continuous column and DWC Table 3.9 Comparison of three distillation models Previous studies xCA ηCA QB/P (cal/kg) Batch column of C.H.Ha et al 0.99 75% 1.2*106 Vacuum distillation Fractional distillation Continuous distillation system 0.9866 86.68% 0.995 85.63% 0.99 0.986 0.99 0.986 _ _ 484138 445071 55 DWC Table 3.9 shows that the batch column in the C.H.Ha study et al has QB/P (cal/kg) greater significantly than the continuous distillation system and DWC (1.2*106 cal/kg compare to 484138 cal/kg and 445071 cal/kg) This indicates that the continuous distillation tower system and DWC have the potential to be scaled up to industry for the purpose of saving energy for the cinnamon cassia oil purifying process 3.6 Determination of the HETP of the various random packing In the chemical industry, the distillation process is widely employed It refers to the process of purifying a mixture containing components with various boiling points The advantages of the packing column are low-pressure drop, great mass transfer efficiency, and high capacity It's especially well-suited to vacuum fractionation applications The performance of packed columns, for distillation or absorption services, is frequently expressed in terms of Height Equivalent to a Theoretical Plate (HETP) or/and Height of Transfer Unit (HTU) For packed columns, a variety of empirical or semi-theoretical mass-transfer models have been reported in the literature There are several models in the literature that use equations or graphs to estimate pressure drop and capacity On the other hand, some models are based on the two-film theory and penetration theory Bravo et al developed the most commonly used model for calculating the HETP or HTU for structured packing, known as the BRF model The authors assumed that the liquid-side mass transfer resistance could be ignored and that HETP could be approximated to the gas-side mass transfer resistance Bravo et al proposed a new version of the previous equations called the SRP (Separations Research Program) model The authors modified the previous assumption about the complete wettability of the packing surface area The SRP model included two corrective factors to predict the effective surface area The first parameter is the surface enhancement factor (FSE) which accounts for variations of surface packing and the second is a correction factor for total liquid hold-up due to effective wetted area (Ft) By using 31 distinct liquid-gas systems and 67 different types of packings, Billet and Schultes, 1993 investigated the mass transfer process into packed columns for gas absorption and distillation operations (BS model) The authors investigated different height and diameter columns, operating in a countercurrent flow with both structured and random packings in this research The penetration hypothesis was also used to both gas and liquid mass transfer The mass transfer model in the gas phase is based on the assumption that gas flows in various directions through the packing and that the contact area between phases must be refreshed after a theoretical time (tG) The packing specific constants, CLBS and CGBS, are dependent on the specific structures and material of the packing 3.6.1 Material of the packing Because separation efficiency not only depends on column packing material but also on the geometry of the packing The material for fabricating different types of packing was SUS-304 stainless steel mesh (50 and 80 mesh corresponding with packing type: 56 M-50, M-80, S-80, and O-80) with technical parameters shown in Table 3.9 Packings were cut and shaped by hand The forms of the different packing with the average sizes were shown in Figure 3.17 For each experiment, the average HETP index is calculated Table 3.10 Technical data of packaging materials Wire diameter (mm) Opening (mm) Opening (%) Overall thickness (mm) Density (g/m2) Stainless steel mesh SUS 304, 50 mesh 0.2286 0.2794 30 0.4572 ~ 267.99 Stainless steel mesh SUS 304, 80 mesh 0.1397 0.1778 31 0.2794 ~ 235.83 Figure 3.17 Various geometric parameters of the packings 3.6.2 Distillation pilot plant The experiment system consists of a still (250 mL round bottom flask) that was heated by a heating mantle for round flasks Two thermometers were set up at the bottom and the top of the distillation system A condenser was cooled by water refrigerant A distillate van and reflux van were designed to control the reflux ratio during the distillation process The column was isolated by glass wool jacket The concentration of n-hexane and cyclohexane were measured by the refractometer Abbe Mark III, Reichert, USA The cinnamaldehyde distillated from cinnamomum cassia oil (99,0%, purchased from Arenex Co Ltd Viet Nam) and benzaldehyde (99.0 % wt., purchased from Arenex Co Ltd Viet Nam) content of the top products and bottom products were determined by Gas Chromatography (GC) method using the SHIMAZU GC2010 plus (FID detector) system The chemicals used were as follows: n-hexane 99%, 57 GHTECH, China (CAS 110-54-3) and Cyclohexane 99.7%, GHTECH, China (CAS 110-82-7) The experiments were performed in a laboratory batch distillation column made from a glass tube with 40 mm of inner diameter and 550 mm long The column was filled with the shaped random packings This column was designed with a liquid dispenser part that was set right above the top of the packing in the column All experiment setup was shown in Figure 3.18 Figure 3.18 Experimental setup for HETP evaluation Heating mantle for round flasks, Still (250 mL round bottom flask), 3,5 Thermometer, Column with shaped random packings, Condenser, Vacuum pump, Valve, Liquid separation can The bottom mixture was heated by a heating mantle to the boiling point, after which the refrigerant fully condenses the vapor at the top of the column The temperature of the reboiler and the top of the column were measured using thermometers The efficiency of the packings is commonly tested by standard mixtures The HETP index of the packing is measured in the paper using an n-Hexane/Cyclohexane mixture One of the major reasons is the high relative volatility of the two components As a result, determining the HETP index is simple At atmospheric pressure (101 kPa), the experiments were carried out with a prepared n-Hexane/Cyclohexane mixture A 100 mL of mixture of the n-Hexane/Cyclohexane with volume ratio (V1:V2) was prepared for distilling This mixture was load into the reboiler and heated by heating mantle When the liquid-vapour equilibrium in the system was stable in about hour, the 58 liquid samples at the top and bottom of the column were collected and analyzed by refractometry The time between the first vapor release and the first sample was almost 60 minutes, and a steady state was considered to be achieved when three successive samples had identical compositions The mole fraction at both the top and bottom were used to calculate the number of theoretical stages (NTS) The mass transfer is reported in terms of the height equivalent of a theoretical plate (HETP) Three case research is performed for each packing type, with the following initial volume compositions: n-hexane (mL):cyclohexane (mL) = V1:V2 = 30:70; 50:50; and 70:30 3.6.3 HETP calculation In order to analyze the mixture of n-hexane and cyclohexane, a calibration curve of the mole fraction of the n-hexane/cyclohexane mixture and the refractive index was built, Figure 3.19 These samples were prepared by mixing and measured by using a refractometer at ambient conditions Figure 3.19 shows that the correlation coefficient between model and experimental values is acceptable with R2 = 0.998 Interpolating from the graph yields the composition of the distillate and bottom products Refractive indices (RI) 1.43 1.42 R² = 0.998 1.41 1.40 1.39 1.38 1.37 0.2 0.4 0.6 0.8 Mole fraction of n-Hexane Figure 3.19 Calibration curve for mole fraction of n-hexane with RI Consider the distillation of cyclohexane/n-hexane at 101 kPa at total reflux, Figure 3.20 shows the relative volatility (avg) with composition for this system calculated using NRTL models by AspenPlus software to estimate constant relative volatilities This calculation was based on the vapor and liquid mole fraction of n-hexane and cyclohexane The volatility of the components can be determined the following equation: 𝐾𝑖 = 𝑦𝑖 𝑥𝑖 59 Where: xi – liquid mole fraction and yi – vapor mole fraction; i = to n; n – number of simulated data Based on the simulated results, we can estimate the average relative volatility of the mixture: 𝐾 ∑𝑛1 𝑛−ℎ𝑒𝑥𝑎𝑛𝑒 𝐾𝑐𝑦𝑐𝑙𝑜ℎ𝑒𝑥𝑎𝑛𝑒 𝛼𝑎𝑣𝑔 = = 1.477 𝑛 Where: avg – Relative volatility of n-hexane and cyclohexane; Kn-hexane – Volatility of n-hexane; Kcyclohexane – Volatility of cyclohexane; n – number of simulated data Figure 3.20 K-value for cyclohexane/n-hexane Different volume fractions and construction types of packing were used in the laboratory distillation column The compositions of the top and bottom liquids were determined by calibration curve of the mole fraction of the n-hexane/cyclohexane mixture and the refractive index, Figure 3.20 The Fenske equation was used to evaluate various HETP values for a part of the column, as shown in Table 3.10 A comparison of the results shows the relationship of mixture composition with HETP index The values of relative volatility and geometrics of the packing types effected to HETP values Therefore, in process design and simulation, the average HETP is assumed to be constant in the distillation column According to experimental data, the HETP values were not significant change when the mesh size increases from type M50 to type M-80 The results can be explained that the opening (%) of two materials 60 are the same (~ 30%) However, with various geometrics of the packing, like M, O, and S geometrics, HETP values were change due to specific packing interfacial area and void fraction as the packing parameters, as they are the most important factors affecting mass transfer for structural packings Table 3.10 shows results of the HETP calculation, and the excellent HETP was obtained by the packing with O geometric (HETPm = 0.045) Table 3.11 HETPm evaluations M-50 V1/V2 xF RID xD RIW xW NTS HETP HETPm 30/70 50/50 0.263 M-80 70/30 30/70 50/50 0.450 0.660 0.263 1.390 1.384 1.384 0.572 0.705 1.421 1.415 0.046 0.137 8.987 7.336 0.045 0.055 0.052 O-80 70/30 30/70 50/50 0.45 0.660 0.263 1.391 1.378 1.384 0.705 0.566 0.87 1.414 1.421 0.148 7.092 0.056 S-80 70/30 30/70 50/50 70/30 0.45 0.660 0.263 0.45 0.660 1.383 1.383 1.380 1.379 1.384 1.389 0.714 0.731 0.743 0.814 0.811 0.698 0.589 1.408 1.411 1.42 1.421 1.405 1.415 1.409 1.417 0.045 0.25 0.205 0.29 6.416 0.092 6.142 0.045 11.14 0.219 8.115 0.06 10.15 0.121 8.984 9.305 5.706 7.167 0.045 0.049 0.065 0.039 0.036 0.062 0.043 0.070 0.056 0.053 0.045 61 0.056 CHAPTER CONCLUSION AND OUTLOOK 4.1 Conclusion This thesis proposed heat integration, which is an application solution to purify Cinnamaldehyde from cinnamon essential oil, with the obtained Cinnamaldehyde purity of 0.99 mass fraction and recovery ratio of 98.60% The first column operates at P1=10mmHg with the following configurations N1=10, NF1=6, R1= 0.30 and the second column operates at P2=20mmHg, N2=59, NF2=31, R2= 3.77 then total heat duty value is minimum QB,total is 1326 cal/s with heat integration Besides, an optimal configuration of the divided wall column is to investigate the same Cinnamaldehyde purity and recovery ratio with continuous distillation models The configuration of DWC are N1=6, N2=14, N3=2, N4=6, N5=14, N6=7 with heat duty is 1219 cal/s In addition to applying this solution to purify cinnamon essential oil, this is a useful solution that can be applied to different processes in the industry 4.2 Outlook - Building the real column of DWC to make experiments to validate the simulation data - Application of the optimal packing into the real distillation columns - Green synthesis of Benzaldehyde from purified Cinnamaldehyde to obtain the higher price of the final product 62 APPENDIX Equilibrium phase data of mixture BA-CA at 10kPa Exp results [17] Calculated results by different models xCA,Exp yCA, Exp T(K) T(oC) yCA, NRTL yCA, Wilson yCA, UNIQUAC yCA, UNIFAC TNRTL(oC) Twilson(oC) TUNIQUAC(oC) TUNIFAC(oC) 1 442.84 169.69 1 1 170.207 170.207 170.207 170.207 0.9458 0.6218 432.52 159.37 0.6535 0.6538 0.65567 0.661 160.664 160.675 160.748 160.926 0.8769 0.3821 422.44 149.29 0.4056 0.406 0.40774 0.4128 150.889 150.912 151.015 151.264 0.8177 0.2727 415.99 142.84 0.2822 0.2827 0.28384 0.2876 144.108 144.139 144.24 144.49 0.7474 0.1879 408.89 135.74 0.1915 0.1919 0.19258 0.1951 137.487 137.526 137.613 137.835 0.6328 0.1151 400.85 127.7 0.1089 0.1092 0.10933 0.1105 129.029 129.074 129.132 129.297 0.5441 0.0853 397.02 123.87 0.0726 0.0728 0.07281 0.0735 123.853 123.897 123.936 124.06 0.4643 0.0623 392.03 118.88 0.0508 0.0509 0.05087 0.0512 119.915 119.955 119.98 120.073 0.3402 0.0386 387.49 114.34 0.0285 0.0286 0.0285 0.0287 114.778 114.806 114.817 114.872 0.2655 0.0282 385.87 112.72 0.0194 0.0194 0.01931 0.0194 112.125 112.145 112.151 112.189 0.1832 0.0181 382.36 109.21 0.0116 0.0116 0.01155 0.0116 109.499 109.511 109.513 109.536 0.1103 0.0104 381.05 107.9 0.0062 0.0062 0.00619 0.0062 107.388 107.392 107.393 107.406 0.0603 0.0056 380.34 107.19 0.0032 0.0032 0.00314 0.0031 106.038 106.04 106.04 106.047 0 377.63 104.48 0 0 104.504 104.504 104.504 104.504 63 Equilibrium phase data of mixture BA-CA at 20kPa Exp results [17] xCA,Exp yCA, Exp 1 T(K) Calculated results by different models T(oC) 463.15 190.15 yCA, NRTL yCA, Wilson yCA, yCA, UNIQUAC UNIFAC 1 TNRTL(oC) Twilson(oC) TUNIQUAC(oC) TUNIFAC(oC) 189.684 189.684 189.684 189.684 0.9621 0.7581 456.72 183.72 0.7795 0.7799 0.78143 0.787 183.535 183.548 183.605 183.778 0.9063 0.5307 448.48 175.48 0.5539 0.5545 0.55648 0.564 175.621 175.649 175.75 176.055 0.7911 0.2799 434.63 161.63 0.2964 0.297 0.29816 0.3035 162.695 162.744 162.855 163.203 0.7721 0.2578 433.18 160.18 0.2696 0.2702 0.27119 0.2761 160.913 160.963 161.071 161.412 0.7203 0.2059 428.74 155.74 0.2101 0.2107 0.21132 0.2151 156.449 156.504 156.6 156.916 0.6454 0.1547 422.86 149.86 0.1493 0.1497 0.15004 0.1525 150.858 150.915 150.991 151.26 0.5188 0.0945 415.23 142.23 0.0861 0.0863 0.08633 0.0875 143.149 143.202 143.247 143.435 0.4656 0.0781 413.16 140.16 0.0684 0.0686 0.06852 0.0694 140.405 140.453 140.487 140.646 0.3415 0.0467 407.83 134.83 0.039 0.039 0.03894 0.0393 134.847 134.881 134.897 134.996 0.2756 0.0343 405.18 132.18 0.0279 0.0279 0.02786 0.0281 132.281 132.306 132.316 132.389 0.1578 0.0171 400.92 127.92 0.0132 0.0132 0.01313 0.0132 128.207 128.218 128.221 128.257 0.0654 0.0068 398.39 125.39 0.0048 0.0048 0.00474 0.0048 125.384 125.387 125.388 125.401 0 123.547 123.547 123.547 123.547 0 396.65 123.65 Equilibrium phase data of mixture BA-CA at 30kPa 64 Exp results [17] Calculated results by different models xCA,Exp yCA, Exp T(K) T(oC) yCA, NRTL yCA, Wilson yCA, UNIQUAC yCA, UNIFAC 1 475.83 202.68 1 1 202.172 202.172 202.172 202.172 0.9612 0.7852 469.67 196.52 0.796171 0.796569 0.798077 0.804399 196.261 196.276 196.335 196.535 0.8823 0.5056 459.19 186.04 0.51734 0.518053 0.520007 0.528992 185.902 185.941 186.055 186.449 0.7911 0.3245 448.74 175.59 0.329233 0.329938 0.331222 0.338234 176.189 176.245 176.365 176.796 0.6999 0.2198 440.46 167.31 0.217392 0.217956 0.218596 0.22327 168.305 168.369 168.47 168.858 0.6442 0.1751 436.52 163.37 0.17079 0.171251 0.171614 0.175155 164.182 164.247 164.332 164.681 0.6049 0.1498 433.87 160.72 0.144562 0.144951 0.14517 0.148058 161.531 161.595 161.67 161.988 0.558 0.1238 430.88 157.73 0.118726 0.119033 0.119124 0.121372 158.609 158.671 158.733 159.016 0.4782 0.0898 426.84 153.69 0.0849097 0.0850936 0.0850541 0.0864984 154.151 154.206 154.25 154.474 0.3402 0.0496 420.48 147.33 0.0460277 0.046059 0.0459529 0.046584 147.645 147.683 147.703 147.84 0.2794 0.037 418.12 144.97 0.0339902 0.0339806 0.0338798 0.0343008 145.158 145.187 145.2 145.305 0.1578 0.0172 412.94 139.79 0.0158346 0.0157906 0.0157276 0.0158873 140.721 140.732 140.737 140.789 0.0603 0.0058 410.5 137.35 0.0052702 0.00524211 0.00521836 0.00526384 137.582 137.585 137.586 137.604 0 408.67 135.52 135.794 135.794 135.794 135.794 0 65 TNRTL(oC) Twilson(oC) TUNIQUAC(oC) TUNIFAC(oC) The GC diagrams of the mixtures in absolute ethanol before and after carrying out the distillation by the batch distillation pilot (a) The initial mixture of cinnamaldehyde and benzaldehyde; (b - d) Top products of the feeding mixture with difference volume compositions: Benzaldehyde (mL):Cinnamaldehyde (mL) = V1:V2 = 30:70, 50:50, and 70:30 of the distillation process (a) Benzaldehyde (b) Cinnamaldehyde Solvent (Ethanol) Benzaldehyde Solvent (Ethanol) (c) (d) Solvent (Ethanol) Solvent (Ethanol) Benzaldehyde 66 Benzaldehyde REFERENCES [1] "Global Natural Cinnamic Aldehyde Market- Industry Analysis and forecast 2020 – 2027: By Application, End-use Industry and Region." 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