- 作者： 曹簡禹; 黃定加
- 作者服務機構： 臺灣省立成功大學化工系
- 中文摘要：
本研究係用續流定床法在離子交換樹脂接觸下，作分解烏頭酸與異戍醇酯化作用之動力學研
究。對此可逆反應在定流狀態及平衡情況時之速度常數，曾作理論研討，並導出數學關係方程式。
由於離子交換樹脂粒子之多孔性，曾對粒子表膜擴散及內孔擴散之阻力，加以詳盡之研討，並導出
理論方程式。
一如上年所研究之非連續法所得之結果，此項連續法亦有兩明顯之二次反應期。前期為單酯之
生成，後期為雙酯之形成。對於研究溫度，分子比及樹脂顆粒影響時，曾作實驗以決定此前後兩期
可逆反應之平衡常數，藉循理論根據，以計算四種速度常數。溫度較高，分解烏頭酸對異戍醇分子
數之比較小，及較小之樹脂粒半徑，或較大之樹脂表面積，皆在一定接觸時間（即樹脂重量除以流
速）之定流狀態下，產生較高之百分生成率。四種速度常數，皆與絕對溫度之倒數，或反應物之當
量比成直線關係。在不同溫度但在定當量比下之活化能及頻率因素，皆按阿崙尼斯（Arrhenius）
方程式計算出來。在恒溫及恒分子比之情況下，四種速度常數之對數皆與樹脂粒子表面積之對數成
直線關係。
表膜擴散隨接觸時間之增加，或流速之降低而增加。但若接觸時間小於 50（克樹脂／毫升。
分 ）時，則無表膜擴散之阻力。內孔擴散在無表膜擴散之範圍內亦曾加以研究。結果發見此種樹
脂粒子之內孔擴散甚為?大。證明此類不均勻之接觸反應中，所有之樹脂接觸劑極為多孔。數 - 英文摘要： In this investigation the esterification of itaconic acid and isoamyl alcoho in thepresence of acid regenerated resin has been studied kinetically in a continuous-flowand fixd-bed process, Theoretical considerations about the rate constants of thisreversible process at steady state and at equilibrium were discussed and mathema-tical equations derived. Because of the porosity of the resin catalyst particles used,authentic discussions with theoretical equations were made on the resistance due tofilm diffusion and pore diffusion. Like batch process, this continuous process was found to be a two stage process,the earlier stage being the monoester formation and the later stage the diester forma-tion. In the study of temperature effect, mole ratio effect and resin particle size effect,particular experiments were done to determine the equilibrium constants for theearlier stage and later stage which were theoretically required for the calulation ofthe four reaction rate constants of the two reversible stage. Higher temperature,smaller mole ratio of itaconic acid to isoamyl alcohol, and smaller size particles orbigger resin surface area, always gave higher percentage conversion at every steadystate of constant contact time, W/F (weight of ersin in reacting column divided bythe flow rate of feed). Linearity was always found for the four reaction rate con-stants with the reciprocal of absolute temperature or equivalent ratio. Energy ofactivation and frequency factore were calculated at different temperatures but constantmole ratio according to Arrhenius equation. There was found a log-log linear relationship between each of the four reaction rate constants and the surface area of theresin particles at constant temperature and mole ratio. Film deffusion was found to increase as the increase of the contact time or asdecrease of flow rate, but there was no film diffusion resistance when the contacttime was less than 50 g.resin/ml‧min . Pore diffusion was studied in the range whenthere was no film diffusion. It was found to be very strong to prove that the resinparticles must be very porous for this king of heterogeneous catalytic reaction.
- 中文關鍵字： --
- 英文關鍵字： --
