| 摘要: | 分離純化的技術在工廠中隨處可見，為了使產品的純度和品質提高，這技術也被廣泛的應用製藥業、礦產業、食品業、石化業等需要純化產品之產業。 我們設計了一套流程，找出一分子（phenazine）可和最終產品(vanillin)產生共晶(1:2 co-crystals of phenazine-vanillin)，藉由高低溫產生共晶(1:2 co-crystals of phenazine-vanillin)，先讓共晶(1:2 co-crystals of phenazine-vanillin)和其他生化反應下副產品(vanillyl alcohol)分離，再利用溶劑篩選的方法，找出可分離共晶(1:2 co-crystals of phenazine-vanillin)的溶劑，使得可共晶之分子(phenazine)和其最終產物(vanillin)分離。 最後我們將甲苯中生成共晶的製程放到連續式共晶且調整不同流速(50、70、 90 ml/min)，探討流速和顆粒大小之關係，發現顆粒大小和流速成反比。且希望藉著分離技術和連續式生產技術的整合，讓工廠純化的步驟有新的選擇。 以下列出我們的貢獻:(1)在甲苯中做出共晶(1:2 co-crystals of phenazine-vanillin)。(2)找到共晶有兩個同素異形體(熔點90oC和97oC)。(3)運用溶劑篩選法找到可分離的共晶的溶劑如甲基第三丁基醚、丙酮、二甲基亞碸和甲醇。(4)藉由降溫法在連續式共晶生產做出共晶(1:2 co-crystals of phenazine-vanillin)。(5)比較連續式共晶和批次共晶發現連續式共晶的產率(51.2%)大於批次共晶產率(34.9%)。(6)計算連續式共晶和批次共晶的晶體生長速率和成核速率的mixed suspension, mixed product removal (MSMPR)，生長速率：批次共晶(4.1×10-4 mm/s)大於連續式共晶(2.6×10-4 mm/s)、成核速率：連續式共晶(2.8×104 no./l∙s)大於批次共晶(3.4×103 no./l∙s)。Separation and purification technologies can be seen in the pharmaceutical industry, mining industry, the food industry, petrochemical industry and other need purgative industry. We have devised a process to use a molecule (i.e. phenazine) which can form co-crystals (i.e. 1:2 co-crystals of phenazine-vanillin) with the final product (i.e. vanillin) by temperature cooling. Co-crystallization of 1:2 co-crystals of phenazine-vanillin can be use to separate vanillin from other by-products such as vanillyl alcohol in bio-based reactions. Initial solvent screening method is also used to identify synthesis solvents and decomplexation solvents of 1:2 co-crystals of phenazine-vanillin. Finally, 1:2 co-crystals of phenazine-vanillin can be prepared in toluene, then we extended it to continuous co-crystallization and adjust different volume flow rates (i.e. 50, 70, 90 ml/min ). We looked at different volume flow rates to see the corresponding change of size distribution. We observed that crystals increased in sizes with the increase in the mean residence time. We hope that through the integration of separation and continuous co-crystallization technology, new options can be provided for manufacturing purification steps. We also list out the significant contributions of this thesis. We made 1:2 co-crystals of phenazine-vanillin in toluene,We found out 1:2 co-crystals of phenazine-vanillin have two different forms with m.p. = 90oC and m.p. = 97 oC,We used solvent screening method to find out that MTBE, acetone, DMSO and methanol can decomplex separate 1:2 co-crystals of phenazine-vanillin,(4) We successfully made 1:2 co-crystals of phenazine-vanillin by continuous co-crystallization by temperature cooling,(5) We compared the mass balance of continuous co-crystallization and batch co-crystallization individually, and continuous co-crystallization has a better yield (51.2%), and the one for batch co-crystallization (34.9%).(6) We calculated crystal growth rates and nucleation rates for continuous co-crystallization with the one of batch co-crystallization. By mixed suspension, mixed product removal (MSMPR) model Growth rate: Batch co-crystallization (4.1×10-4 mm/s) > continuous co-crystallization (2.6×10-4 mm/s). Nucleation rate: Continuous co-crystallization (2.8×104 no./l∙s)> batch co-crystallization (3.4×103 no./l∙s). |
