Please use this identifier to cite or link to this item: http://hdl.handle.net/11455/3603
DC FieldValueLanguage
dc.contributor王茂齡zh_TW
dc.contributor吳和生zh_TW
dc.contributor鄭紀民zh_TW
dc.contributor謝育民zh_TW
dc.contributor.advisor楊鴻銘zh_TW
dc.contributor.author陳建行zh_TW
dc.contributor.authorChen, Chien-Hsingen_US
dc.contributor.other中興大學zh_TW
dc.date2008zh_TW
dc.date.accessioned2014-06-06T05:32:15Z-
dc.date.available2014-06-06T05:32:15Z-
dc.identifierU0005-0407200712210600zh_TW
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dc.identifier.urihttp://hdl.handle.net/11455/3603-
dc.description.abstract本研究探討以超音波輔助三液相相間轉移觸媒催化鄰-羥¬基苯甲酸鈉與溴丁烷合成鄰-羥苯甲酸正丁酯之酯化反應,三液相催化系統於特定條件下能析出一相促進反應的進行。超音波化學是利用超音波促進化學反應的技術,可提供反應所需的熱量以利反應的進行。本研究內容包括合成鄰-羥苯甲酸正丁酯之動力學研究,本系統反應條件之最適化,以及超音波振盪、攪拌混合與結合兩種效應之比較。 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 %。zh_TW
dc.description.abstractThe 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.en_US
dc.description.tableofcontents中文摘要------------------------------------------------------------------------------ i 英文摘要------------------------------------------------------------------------------ ii 誌謝------------------------------------------------------------------------------------ iv 目錄------------------------------------------------------------------------------------ v 圖目錄--------------------------------------------------------------------------------- vii 表目錄--------------------------------------------------------------------------------- x 符號說明------------------------------------------------------------------------------ xii 第一章 緒論 1 一﹑前言--------------------------------------------------------------------- 1 二﹑相間轉移觸媒反應--------------------------------------------------- 2 三﹑第三液相觸媒催化反應--------------------------------------------- 13 四﹑酯化反應--------------------------------------------------------------- 18 五﹑超音波原理及應用--------------------------------------------------- 21 六﹑研究目的與研究方法------------------------------------------------ 27 第二章 實驗藥品與設備 30 一﹑實驗藥品--------------------------------------------------------------- 30 二﹑實驗裝置與儀器------------------------------------------------------ 31 三﹑產物之合成------------------------------------------------------------ 33 四﹑觸媒中間體之製備--------------------------------------------------- 33 五﹑校正曲線--------------------------------------------------------------- 34 六﹑第三液相觸媒中間體之定量方式--------------------------------- 38 七﹑反應動力實驗步驟--------------------------------------------------- 39 第三章 超音波輔助三液相觸媒催化合成鄰-羥苯甲酸丁酯反應 40 一﹑前言--------------------------------------------------------------------- 40 二﹑第三液相與本質反應----------------------------------------------- 41 三﹑反應機構與動力學模式推導-------------------------------------- 47 四﹑不同相間轉移觸媒及用量對反應之催化活性----------------- 56 五﹑水相與有機相反應物用量之效應-------------------------------- 66 六﹑不同鹽類與溴化鈉添加量之效應--------------------------------- 74 七﹑溶劑種類與水相反應物用量之效應------------------------------ 78 八﹑超音波操作頻率之效應--------------------------------------------- 83 九﹑反應溫度之效應------------------------------------------------------ 90 十﹑結論--------------------------------------------------------------------- 97 第四章 三液相觸媒催化合成鄰-羥基苯甲酸丁酯操作變數中之最適操作條件 98 一﹑三液相觸媒合成鄰-羥基苯甲酸丁酯操作變數中之最適操作條件探討----------------------------------------------------------- 98 (一) 控制變因的決定----------------------------------------------- 99 (二) 操作變因之探討及選用---------------------------------------- 104 二﹑超音波振盪、攪拌轉速與結合兩種操作之效應-------------- 115 (一) 超音波頻率之效應------------------------------------------- 116 (二) 攪拌轉速之效應---------------------------------------------- 123 (三) 結合超音波振盪與攪拌轉速之效應---------------------- 128 三﹑結論-------------------------------------------------------------------- 135 第五章 總結 137 參考文獻------------------------------------------------------------------------------ 140 附錄------------------------------------------------------------------------------------ 145zh_TW
dc.language.isoen_USzh_TW
dc.publisher化學工程學系所zh_TW
dc.relation.urihttp://www.airitilibrary.com/Publication/alDetailedMesh1?DocID=U0005-0407200712210600en_US
dc.subjectPhase-transfer catalyticen_US
dc.subject相間轉移觸媒zh_TW
dc.subjectThird-liquid phaseen_US
dc.subjectesterificationen_US
dc.subjectultrasounden_US
dc.subjectsonochemistryen_US
dc.subjectcavitationen_US
dc.subject酯化反應zh_TW
dc.subject第三液相zh_TW
dc.subject超音波zh_TW
dc.subject超音波化學zh_TW
dc.subject空穴效應zh_TW
dc.title超音波輔助三液相相間轉移觸媒合成鄰-羥基苯甲酸丁酯之反應動力學研究zh_TW
dc.titleKinetics for Synthesizing o-Hydroxybenzoic Acid Butyl Ester via Ultrasound Assisted Tri-Liquid Phase-Transfer Catalysisen_US
dc.typeThesis and Dissertationzh_TW
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