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Kinetics for Synthesizing o-Hydroxybenzoic Acid Butyl Ester via Ultrasound Assisted Tri-Liquid Phase-Transfer Catalysis
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觸媒溴化四丁基銨、溴化四丁基鏻能順利形成第三液相。有機相反應物溴丁烷用量增加時，反應性提升；使用過量時產率變化量與有機相反應物用量無關。本系統中頻率越低，可獲得較高的產率，超音波頻率28 kHz操作下，反應3小時可獲得82.3 %的產率，並由實驗數據可得第三液相中觸媒中間體的增益比率(η)與有機相中產物的關係式： ，由實驗數據可得虛擬一階動力式 ，反應溫度50~80 ℃範圍內，所求得的活化能為31.5 kJ/mol。
由實驗針對各變數影響作篩選，以提高產率、成本效益、利於分析為前提，於超音波條件： 300 W；28 kHz、反應溫度70 ℃下可得97.33 ％。超音波振盪操作時，頻率越高提供反應的能量減少，導致反應速率也變慢。攪拌操作時，攪拌混合可提高分子間的碰撞機率，克服相與相之間的質傳阻力，使得反應速率由本質反應決定。當結合超音波振盪與攪拌兩種操作時，反應性可大幅提升。攪拌系統中，攪拌轉速超過100 rpm時可克服質傳阻力，當加入超音波輔助時，可更進一步提高產率，增加反應速率，視反應速率常數可提升約53.3 %。|
The kinetics of esterification of sodiume salicylate with butyl bromide to produce salicylic acid n-butyl ester were investigated via ultrasound-assisted tri-liquid phase-transfer catalysis. Third-liquid phase was formed with high catalytic intermediates to increase reaction rate. Sonochemistry is a technique to increase chemical reaction rate by ultrasounic irradiation. Ultrasonic irradiation can provide energy to promote the reaction. The subject of this research involves kinetics for synthesizing o-hydroxybenzoic acid butyl ester, the optimum condition of the reaction system, comparisons between ultrasound-assisted, stirring mixing and both operations. Only tetrabutylphosphonium bromide(TBPB) and tetrabutylammonium bromide(TBAB) can form third-liquid phase among the four catalysts tested in this study. Reaction activity increases with increasing organic reactant concentration as butyl bromide added but keeps constant with largely excess amounts. Activity increases with decreasing ultrasonic frequency. Using ultrasonic frequency 28 kHz the production yield was 82.3 % within 3 hours. Correlating the experimental data, the relation of the enhancement ratio (η) of ArCOOQ in third-liquid phase, and the product yield in organic phase is . The pseudo-first-order kinetic model was used to well describe the overall reaction, by the equation , and the apparent reaction rate constants (kapp) were obtained for with different conditions. We can obtain the activation energy of 31.5 kJ/mol by Arrehenius equation during 50~80 ℃. For high product yield, cost, easy analysis, the production yield was 97.3% as ultrasonic frequency 28kHz, power 300W, and 70℃. With ultrasound alone, the activity becomes lower the energy of higher frequency decreases quickly. Molecule collision raised by agitation can overcome mass transfer resistance. Combining two operations of ultrasound and agitaion make the activity better than with each single operation. Mass transfer resistance can be neglected by stirring speed more than 100 rpm, the yield increases and kapp increases 53.3 % as ultrasound assisted extra.
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