結論

本研究根據混合丁戊醇轉酯化穩態流程設計建構動態控制架構並探討其現 象。根據順序列出以下幾點：

1. 該穩態設計架構具有多重穩態的現象，亦即相同的操作條件下具有許多穩態 點並且各自有不同的產品輸出結果；而以水相回流分率變化作圖發現原本的 最適化操作點(水相回流分率等於 0.66)位於多重穩態中的轉折點，造成動態操 作上的困難。

2. 傳統的庫存控制環路架構(Inventory A)無法應付+1%的 FR 脈衝測試，亦即穩 定範圍較小可能不利於動態操作，所以改用較為特殊的庫存控制環路架構 (Inventory B)。

3. 較保守的操作點(水相回流分率等於 0.75)可以應付到+15%的酸進料純度干 擾，+25%和-15%的混醇進料流量干擾，以及+40%和-30%的混醇進料比例干 擾；且動態響應佳，操作性可應付工廠實際需求，但是因為較保守年度總成 本比最適化的操作點(水相回流分率等於 0.66)高出 12%。

4. 次保守的操作點(水相回流分率等於 0.7)的年度總成本只比最適化的操作點(水 相回流分率等於0.66)高出 7%；但應付干擾的能力較差，響應也慢，干擾排除 範圍較小，實際工廠操作上可能較有困難。

5. 水相回流分率與可操作範圍之間的關係並不明確，需要進一步使用其他方法 測試。

附錄 A TAC 計算公式 250 Btu

U

_{R 2 R}

=

^o

A.5. 蒸餾塔主體價格計算

8150 hr

Q

附錄 B 酯化反應熱力學及動力學模式

mole fraction temp.°C mole fraction temp.°C

*BuOH/BuAc/H2O (0.0726, 0.224, 0.7034) 90.38 (0.0912, 0.2142, 0.6946) 90.44

*BuAc/H2O (0.299, 0.701) 91 (0.2871, 0.7129) 90.98

B.3. Correlation by Hayden-O＇Connell model

RT

B.4.

混合醇酯化系統氣相結合參數列表

Component HAc BuOH AmOH BuAc AmAc H2O HAc 4.5 2.5 - 2 - 2.5 BuOH 2.5 2.2 - 1.3 - 1.55 AmOH - - - BuAc 2 1.3 - 0.53 - 1.3 AmAc - - -

H2O 2.5 1.55 - 1.3 - 1.7

B.5. 乙酸丁酯、丁醇與水之蒸餘曲線圖(Residual Curve Maps)

B.6. NRTL Model 公式

Source Regression Regression Regression Chiang Chiang Aij 13.513 0 -2.909 0 0

Source Aspen Regression Aspen Regression Regression

Aij 0 1.2268 0 0 -0.039

Source Chiang Regression Aspen Regression Chiang

aij 0 0 0 -5.519 0

aji 0 0 0 -6.472 0

bij (K) -144.8 57.328 128.17 2428.1 254.47 bji (K) 320.65 1424.8 -113.6 3774.4 2221.5 cij 0.3009 0.2869 0.3 0.3116 0.2

B.8. 丁醇、戊醇與乙酸之反應動力學式與參數

System k1

(T=402K)

Keq

(T=402K) (1) BuAc

2.23×10^-3

[kmole/(kgcat·s)] 9.75 ( Pseudo-homogeneous model )

r

=

m

cat

( k

₁

a

HAc

a

BuOH −

k

₋₁

a

BuAc

a

H₂O

)

k

1=3.3856×10⁶exp(-70660/RT),

k

-1=1.0135×10⁶exp(-74241.7/RT) (2) AmAc

5.9×10^-6

[m³/(kmol·kgcat·s)] 2 ( Quasi-homogeneous model )

r

=

m

cat

( k

₁

C

HAc

C

BuOH −

k

₋₁

C

BuAc

C

H₂O

)

k

1=31.1667exp(-51740/RT)

k-1=2.2533exp(-45280/RT)

R=8.314 [kJ/kmol/K], T [K], r [kmol/s], m

cat

[kg

cat

], C

i

[kmol/m

³cat

](1)Gangadwala et al.

(2003);(2)Lee et al.(1999)

附錄 C 符號與縮寫說明

符號或縮寫 英文全稱 中文說明

AmAc Amyl acetate 乙酸戊酯

AmOH Amyl alcohol (Pentanol) 戊醇

ASR Aqueous Split Ratio 水相回流分率 BuAc Butyl acetate 乙酸丁酯

BuOH Butanol 丁醇

CS Control Scheme 控制架構

DC Dimeter of column (蒸餾裝置之)直徑

Dec. Decanter 分相槽

Dist. Column Distillation Column (普通)蒸餾塔

F

(mole) Flow rate (莫爾)流量 FC Flow rate Controller 流量控制器

FR Feed Ratio 混醇與酸之進料莫爾比

FT Flow rate Transmitter 流量訊號轉換器

Fb RD bottom mole flow rate 反應蒸餾塔底出料流量

HAc Acetic acid 乙酸

K Gain array 增益矩陣

KC Gain of controller 控制器之增益

Ki,j gain of input i to output j 輸入i 對輸出 j 的增益 LC Level Controller 液位控制器

LT Level Transmitter 液位訊號轉換器

NF Feed tray 進料板

NRG Non-square Relative Gain 非方形相對增益矩陣 NR

Number of trays in rectifying

section (蒸餾裝置之)精餾段板數

Nrxn Number of trays in reactive section (反應蒸餾塔之)反應段板數

NS

Number of trays in stripping

section (蒸餾裝置之)汽提段板數

NT Total number of trays (蒸餾裝置之)總板數 PC Pressure Contorller 壓力控制器

PT Pressure Transmitter 壓力訊號轉換器 Qc Condenser duty 冷凝器負載 Qr (or QReb) Reboiler duty 再沸器負載 RD Reactive distillation column 反應蒸餾塔 RR Reflux Ratio of Dist. column 蒸餾塔之迴流比 Spec. Design Specification 設計規格

SVD Singular Value Decomposition 奇異值分解法 TAC Total Annual Cost 年度總成本 TC Temperature Controller 溫度控制器 TT Temperatur Transmitter 溫度訊號轉換器 Ti Temperature of tray i 第i 板之溫度

x

i

liquid mole composition of

component i 成份

i 之液相莫耳組成

ΔT delta Temperature 溫度變化

Λ (or RGA) Relative Gain Array 相對增益矩陣

τI Integral time constant of controller 控制器之積分時間常數 λi,j relative gain of input i to output j 輸入i 對輸出 j 的相對增益

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作者簡介

姓名 郭紘睿

出生地 台灣台南市

出生日 民國 75 年 2 月 14 日

學歷 台南市立公園國民小學

台南市立後甲國民中學 國立台南第一高級中學

國立台灣大學化學工程系學士

國立台灣大學化學工程所碩士

在文檔中 混合丁戊醇酯化反應蒸餾系統之控制架構研究 (頁 121-134)