臺灣博碩士論文加值系統

蒸餾固化法是一新式的分離純化方法，簡稱為DF法，本論文中在研究分離沸點相近的混合物。DF法結合了蒸餾與結晶的技術，低耗能、可一次性得到高純度產品以及純化成本低廉則為其優點，原理上其是利用液體操作在三相區，液體一部分汽化一部分固化最終得到無母液附著之高純度固體結晶，此固體結晶即為我們所要的產物。在純化過程中，液體操作在絕熱條件下而液體結晶時所釋放出的結晶熱提供液體汽化所需之汽化熱。當DF法應用在方離苯乙烯+乙基苯混合物時，由實驗可知90％的苯乙烯進料可以很容易的純化至96％，但在96％至99％純度的提升上與之前純化的情況比較起來則是困難的；而應用在乙晴+丙烯晴混合物方面，乙晴可以很容易的從93％的乙晴進料中純化至99％，在此混合物純化丙烯晴中，我們則需要以連續不段的三個純化階段才能從95％純化至99％。

A new separation technique, called distillative freezing (DF), is studied in this research to separate mixtures with the close boiling temperatures. In principle, DF is a technology combining distillation and crystallization. In application of DF, the liquid mixture is operated at triple point condition, in which a pure compound is crystallized through crystallization and vapor of mixture is formed through distillation. It results in the formation of pure solid and liquid phase and vapor phase of mixtures. The process is continued until the liquid phase is completely eliminated and only the pure solid crystals remain in the feed. The vapor of mixture formed in the process is condensed and removed. As the DF process is conducted under an adiabatic condition, the latent heat released in forming the solid crystals is mostly removed by vaporizing portions of liquid mixtures. DF is applied here to separate styrene from the styrene+ethylbenzene mixture. It is found that one batch DF operation can purify styrene from 90% to 96~97% in the styrene-enriched mixture. However, two batch DF operations are required to further purify styrene to >99%. DF is also applied to separate the acetonitrile+acrylonitrile mixture. It is found that one batch DF operation can purify acetonitrile from 93% to >99% in the acetonitrile-enriched mixture. On the other hand, three batch DF operations are required to purify acrylonitrile from 95% to >99% in the acrylonitrile-enriched mixture.

目錄
指導教授推薦書
口試委員會審定書
授權書……………………………………………………………Ⅲ
誌謝………………………………………………………………Ⅳ
中文摘要…………………………………………………………Ⅴ
英文摘要…………………………………………………………Ⅵ
目錄………………………………………………………………Ⅶ
圖表目錄…………………………………………………………Ⅷ
第一章 緒論……………………………………………………1
第二章 文獻回顧………………………………………………2
2-1 研究動機………………………………………………2
2-2 苯乙烯簡介……………………………………………3
2-3-1 苯乙烯生產介紹………………………………………6
2-3-2 乙苯脫氫選擇性氧化法(SMART)法…………………6
2-4 現今製程苯乙烯之製造方法…………………………9
2-5-1 乙晴與丙烯晴介紹……………………………………17
2-5-2 丙烯晴製造……………………………………………20
2-5-3 乙晴製造………………………………………………22
第三章 蒸餾固化法……………………………………………24
3-1 蒸餾固化法介紹………………………………………24
3-2 蒸餾固化法的分離原理………………………………24
3-3 蒸餾固化法的優點與特色……………………………25
3-4 相圖的繪製……………………………………………27
3-5 DF操作條件計算………………………………………33
第四章 實驗設備與方法………………………………………37
4-1 實驗藥品與設備………………………………………37
4-2 蒸餾固化設備的周邊裝置……………………………38
4-3 桌上型蒸餾固化設備…………………………………42
4-4 液態氮蒸餾固化設備…………………………………48
4-5 氣相層析儀(GC)分析條件……………………………52
4-6 實驗方法………………………………………………52
4-7 校正曲線製作…………………………………………53
第五章 結果與討論………………………………………………55
5-1 苯乙烯-乙基苯雙成分DF實驗…………………………55
5-2 苯乙烯-乙基苯雙成分多階段DF實驗………………… 56
5-3 乙晴-丙烯晴雙成分DF實驗……………………………68
5-4 乙晴-丙烯晴雙成分多階段DF實驗……………………68
第六章 結論………………………………………………………77
參考文獻………………………………………………………………79
附錄一…………………………………………………………………81
附錄二…………………………………………………………………83

Cavani, F., & Trifiro, C. (1995), Alternative process for the
production of styrene, Applied catalysis A, 133, 219-239.
Kirk, R. E., & Othmer, & D. E., Eds. (1991), Encycleopedia of
chemical technology, 1, 352-369.
Kirk, R. E., & Othmer, & D. E., Eds. (1991), Encycleopedia of
chemical technology, 22, 956-994.
“Mathcad Version 8”, Mathsoft Apps.
NIST Standard Reference Database 11, (1985), DIPPR data compilation
of pure compound properties, version 5.0; sponsored by The Design
Institute for Physical Property Data (DIPPR) of the American
Institute of Chemical Engineers; The American Institute of
Chemical Engineers: New York.
Shiau, L. D., & Wen, C. C., & Lin, B. S. (2005), Separation and
purification of p-xylene from the mixture of m-xylene and p-xylene
by distillative freezing, Ind. Eng. Chem. Res., 44, 2258-2265.
Shiau, L. D., & Wen, C. C., & Lin, B. S. (2006), Application of
distillative freezing in the separation of o-xylene and p-xylene,
AIChE Journal,52, 1962-1967.
Godbole, S. P., & Wappelhorst, R. L., & Jacobson, P. A. (2001),
Purification and recovery of acetonitrile, U.S. Patent 6326508B1.
林柏學, (2005), 利用蒸餾固化法純化對二甲苯, 長庚大學化工與材料工程研究所, 碩
士論文.
呂登復, (2003), 實用真空技術, 國興出版社, 新竹, 一版四刷.
謝咏潾, (1999), 蒸餾固化製程之模擬與應用, 長庚大學化工與材料工程研究所, 碩士
論文.
溫俊清, (2002), 以蒸餾固化法純化對-苯二甲酸, 長庚大學化工與材料工程研究所, 碩
士論文.
化工技術編輯部, (2005), 化工技術, 越吟出版社, 台北