臺灣博碩士論文加值系統

相間轉移催化反應系統的研究，一直是近年來化工界研究的重點。對於某些相間轉移觸媒催化反應系統，在反應過程中，會有第三液相出現。第三液相的生成，可使得反應速率大幅增加，同時，也使得產物的分離步驟簡化。在化工界的應用方面，此類系統具有很大的潛力，其分散特性也是很重要的設計資料。
系統的穩定性是反應器的重要設計條件。當分散相越多，質傳面積越大，液滴結合速率越快，即可能產生相轉換，亦即分散相變為連續相，連續相變為分散相。過去有關相轉移觸媒反應的相關應用與研究，包括第三液相生成的探討，大多以四級銨鹽為主。但是四級銨鹽在某些極端的條件下會發生Hofmann Degradation。而四級磷鹽的催化效率並不會遜於四級銨鹽，且在一般反應條件下比四級銨鹽更穩定。因此本論文以溴化四丁基磷做為相轉移觸媒，催化有機相中的苯甲醯氯和水相中的酚鈉合成苯甲酸苯酯。並透過電導度法來探討觸媒濃度和反應物濃度對於系統的物性、相轉換Hold-Up、第三液相生成量、液滴結合時間和遲滯相轉換時間的影響。由實驗所得結果發現於高觸媒濃度的系統中，不論是W/O -> O/W或O/W -> W/O，相轉換Hold-Up皆會隨著觸媒濃度上昇而下降，而攪拌速率增加也會降低系統的相轉換Hold-Up。在高觸媒濃度下，含水相反應物的系統，相轉換Hold-Up會隨著水相反應物濃度的增加而下降；對於含有機相反應物的系統而言，相轉換Hold-Up隨有機相反應物濃度的改變卻是相反的趨勢。除此之外，在含兩相反應物的系統中，系統的相轉換Hold-Up會隨著兩相反應物濃度上昇而下降。
在影響第三液相生成的因素方面，第三液相的生成量隨著觸媒及兩相反應物濃度上昇而增加。實驗的結果也發現攪拌動力對第三液相的生成量也有一定程度的影響。在低轉速的攪拌下，不容易有第三液相的生成，隨著攪拌速率的增大，系統更易生成第三液相。除此之外，系統的組成也與第三液相的生成有關。在添加物方面，隨著NaOH添加量的改變，第三液相的生成量會有不同的變化。而NaOH的添加會使系統相轉換Hold-Up有些微的下降。
一般而言，有第三液相生成的系統和添加NaOH的系統，系統的Tc值會比其他系統較長。而對大部分系統而言，O/W分散型態的Tc值比W/O分散型態較長。

Recently many researches have been dedicated to the phase transfer catalysis reaction systems. In some of these systems, the formation of the third liquid phase（TLP） dramatically accelerates the reaction rate and simplifies the separation process. Studies on this field will be of great potential in the industry. Dispersion characteristics of these systems involving two or three immiscible liquids are also very important for the design of chemical processes.
The stability of the system is of much importance in the design of chemical processes. Increasing the volume fraction of the dispersed phase will result in the increase of the mass transfer areas, promote the drop coalescence rate and eventually lead to the occurrence of phase inversion, i.e. the dispersed phase becomes the continuous phase and vice versa.In the past, quaternary ammonium salts have been used in the majority of reports on phase transfer catalysis reactions or third liquid systems, but it may undergo decomposition reaction under some extreme conditions of high temperatures or concentrated bases, like Hofmann degradation. Under the same reaction conditions, quaternary phosphonium salts can be equally effective and more stable.Thus, we use tetrabutylphosphonium bromide as catalyst to catalyze the synthesis of phenyl benzoate from benzoyl chloride in the organic phase and sodium phenolate in the water phase. In this text, the method of electrical conductivity was used to investigate the effect of concentrations of the PTC and reactants upon the phase transfer characteristics of the TLP systems, volume of the TLP, droplet coalescence time and the delayed inversion time. We found that in the systems with higher concenrations of PTC, no matter for W/O -> O/W or O/W -> W/O, phase inversion Hold-Up would decrease with increasing contentrations of PTC and stirrer speeds. Phase inversion hold-up would decrease with increasing concentrations of water phase reactant, but it become reverse for the increasing concentrations of organic phase reactant. Besides, phase inversion hold-up of the systems decrease with increasing concentrations of the both phase reactants.
For the factors which affect the formation of the third liquid phase, the amount of the TLP formed increaes with increasing concentrations of PTC and both phases reactants. We also found that stirrer speed affected the amount of the TLP formed and TlP were easier to be formed under higher stirrer speeds. In addition, the formation of the TLP also have relations with the composition of the system. For the systems with NaOH added, the amount of TLP formed changes inconsistently with increasing amounts of NaOH. In such systems, phase inversion hold-up decrease slightly.
In general, the Tc values of the systems contain the TLP or NaOH are higher than those of the other systems. For the most systems, the Tc values of the O/W dispersion type are higher than those of the W/O dispersion type.

第一章 緒論...............................................1
1.1研究動機............................................1
1.2文獻回顧............................................2
1.2.1兩液相反應系統.................................2
1.2.2相間轉移觸媒及其反應機制.......................8
1.2.3相間轉移觸媒種類..............................11
1.3論文架構...........................................13
第二章 實驗方法..........................................14
2.1實驗裝置...........................................14
2.2實驗藥品...........................................18
2.3實驗步驟..............................................18
2.3.1清洗步驟......................................19
2.3.2相轉換Hold-Up的測定...........................19
2.3.2.1無觸媒及兩相反應物存在的系統.............19
2.3.2.2只有觸媒存在的兩相系統...................20
2.3.2.3添加觸媒及水相反應物的系統...............21
2.3.2.4添加觸媒及有機相反應物的系統.............21
2.3.2.5觸媒及兩相反應物皆存在的系統.............21
2.3.2.6觸媒及兩相反應物皆存在並添加NaOH的系統...22
2.3.3液滴結合時間（Tc）的測定......................22
2.3.4遲滯相轉換時間（Td）的測定....................23
2.3.5系統物性的量測................................23
2.4數據處理...........................................24
第三章 結果與討論........................................26
3.1純水-正己烷的系統..................................26
3.2添加溴化四丁基磷的系統.............................39
3.2.1只添加觸媒的系統..............................39
3.2.2添加觸媒及水相反應物的系統....................57
3.2.3添加觸媒及有機相反應物的系統..................68
3.2.4添加觸媒及兩相反應物的系統....................77
3.2.5有第三液相生成的系統..........................97
第四章 結論.............................................112
參考文獻................................................115

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