臺灣博碩士論文加值系統

反應蒸餾法為一個有效的粗乳酸純化分離方法，可藉由加入正丁醇進
行酯化反應，將所生成的乳酸正丁酯再進行水解反應，以獲得高純度乳
酸。本研究建立了批次式反應蒸餾的實驗裝置，並進行了一連串乳酸酯化
與乳酸正丁酯水解之反應蒸餾實驗，酯化過程中配以不同比例之正丁醇與
乳酸之進料來進行批次式反應蒸餾，水解實驗則以不同比例之水與乳酸正
丁酯進料於真空條件下(4.5KPa)進行批式反應蒸餾，二者塔頂冷凝液皆流
經一分相器，前者為有機相回流，後者為水相回流，每0.5~1小時取樣並收
集了相關實驗操作數據，最終可得到乳酸濃度88wt%。在另一方面，參考
了陳正瀚(2010)所得到之乳酸、正丁醇、乳酸正丁酯、水等四成分相關系
統之相平衡數據，並加入含高濃度乳酸(≦90wt%)之汽液相平衡數據，以
NRTL模式迴歸得到了相關二元交互作用參數，並以ASPEN軟體模擬上述
之酯化與水解批式反應蒸餾程序，二者模擬與吾人實驗結果相當吻合，從
而驗証了使用之熱力學參數之正確性，以及以反應蒸餾生產乳酸製程之可
行性。

Reactive distillation can be an effective means for purification of crude
lactic acid. It can be achieved by esterification of crude lactic acid with
n-butanol, followed by hydrolysis of butyl lactate. In this study, the feasibility
of reactive distillation for esterification and hydrolysis reactions was evaluated
through batch reactive distillation experiments. Esterification process was
accomplished by batch reactive distillation using different n-butanol to lactic
acid feed ratios, while hydrolysis process was conducted at vacuum condition
(4.5kPa) with different water to butyl lactate feed ratios. In both esterification
and hydrolysis experiments, part of the condensate of overhead vapor was
recycled to the column via a decanter. It was in the form of an organic-phase
reflux in the former case. In the batch hydrolysis column, it was in the form of
an aqueous-phase reflux. Experimental data were collected every 0.5~1 hour.
On the other hand, Chen’s (2010) experimental vapor-liquild equilibrium (VLE)
data were employed, and high lactic-content VLE data for the lactic
acid/n-butanol/water/n-butyl lactate system were obtained and regressed with
the NRTL model to yield binary interaction parameters for the system, which
were subsequently used in simulating the batch reactive distillation processes
with Aspen Plus, and simulation results agreed well with the experimental
results, thereby verifying the applicability of the thermodynamic parameters
and the feasibility of the purification of lactic acid by reactive distillation.

Abstract............................................................I
摘要.........................................................................II
目錄..................................................................III
圖目錄..........................................................VI
表目錄................................................................X
第一章緒論........................................................................1
1.1 前言.........................................................................1
1.2 研究動機................................................................1
1.3 論文組織與架構...............................................5
第二章文獻回顧.................................................................6
2.1 反應蒸餾..................................................................6
2.2 反應蒸餾塔之程序分析.........................................7
2.3 酯化水解系統之反應蒸餾........................................9
2.4 殘餘曲線.................................................................10
2.5 批式反應蒸餾...........................................................14
2.6 反應蒸餾法純化乳酸....................................................14
第三章熱力學與動力學模式................................................17
3.1 熱力學模式...........................................................17
3.1.1 相平衡實驗數據......................................................19
3.1.2 迴歸方法與結果.......................................................26
3.2 動力學模式.............................................................42
第四章實驗方法與步驟.....................................................44
3.1 實驗藥品.................................................................44
3.2 樣品分析方式..........................................................45
3.2.1 氣相層析儀分析...........................................45
3.2.1.1 定性分析...........................................46
3.2.1.2 定量分析............................................46
3.2.2 檢量曲線......................................................46
3.3 動態再循環式汽液相平衡實驗...............................51
3.3.1 實驗裝置.........................................................51
3.3.2 汽液相平衡實驗步驟..........................................52
3.4 批式酯化反應蒸餾實驗.................................................53
3.4.1 實驗裝置..........................................................53
3.4.2 實驗步驟........................................................54
3.5 批式水解反應蒸餾實驗.......................................55
3.5.1 實驗裝置........................................................55
3.5.2 實驗步驟.......................................................56
第五章反應蒸餾分析................................................58
5.1 殘餘曲線圖....................................................58
5.2 反應蒸餾實驗數據..................................................61
5.3 反應蒸餾模擬......................................................68
5.4 結果與討論..................................................78
第六章結論.........................................................98
參考文獻........................................................104
附錄 A 座標轉換....................................................109
附錄 B Components´ Antoine Parameter..................................110
附錄 C 液液相平衡......................................................111

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陳正瀚，「四成份反應系統之相平衡探討：乳酸-正丁醇-水-乳酸正丁酯」，
私立東海大學化學工程所碩士論文(2010) .