臺灣博碩士論文加值系統

近年來結合反應與分離功能的反應性蒸餾製程重新受到重視。本研究的目的在於繼續探討異相反應蒸餾系統(或三相的反應蒸餾系統)。所謂的異相反應蒸餾即為迴流槽中有兩個液相的存在，利用分相槽(decanter)可以有效的分離出水相及有機相。以酯化系統來說，通常重醇類的酯化系統，如：乙酸丙酯、乙酸丁酯、乙酸戊酯及丙酸丁酯，是較適合異相的反應蒸餾系統。它們有以下三個共同的特點：(1)有較大的兩相區域存在，(2)在兩相區上有一個三成份的最小共沸點，(3)所有的液液平衡線(tie line)最後會回歸於單一產物(如：水)。因此在判斷一正確的製程時，我們可以由其相的分離情形和最小共沸點的座落位置來決定。熱力學模式可以提供相的分佈情形及所有的共沸點組成，進而分類出各種典型的兩相區系統。所以在熱力學模式與參數的選擇上也變得非常重要。以乙酸戊酯為例，若在熱力學的描述不符合以上三個特點，則必須以另一無分相槽的製程設計來進行。
接下來引用郭建麟(2001)所提出的設計步驟，將其延伸至丙酸丁酯的異相反應蒸餾系統。利用不同區段的板數變化及改變進料板的位置對於反應蒸餾塔的年總成本(TAC)影響，找出最適化的設計製程。我們的製程設計上有四個步驟：(1)設定控制目標，(2)選擇控制器變數，(3)決定控制架構，(4)找出控制器配對。由於塔頂的濃度由液液平衡線決定，所以直覺上這是一個單數的控制系統。但Luyben(2000)中指出，需控制內部進料組成以避免反應物供給失衡。最後針對組成或溫度我們提出一控制架構的設計方法。以RGA方法計算控制器配對，ATV調協計算控制器參數。溫度控制方面，以NRG找出溫度設定點。溫度控制的結果顯示，其產品的純度上所些微的偏差，因此利用前饋控制來消除偏差值。控制結構對於進料二股流量有較大的負干時，無法進行控制。這是由於反應效能提高，造成塔頂位置中的液相組成提前進入兩相區域。我們在其正丁醇的進料位置上加一分離控制器(Split range control)環路設計，使系統對干擾的承受程度能有明顯的改善。結果顯示，在有效的控制範圍下，我們可以得到不錯的控制品質。

Abstract
Reactive distillation offers an attractive alternative for process intensification, especially for reaction/separation systems. In this work, we continue the effort to explore a specific class of reactive distillations: heterogeneous reactive distillation (or three-phase reactive distillation). By heterogeneous reactive distillation, we mean two-liquid phase exists in the reflux drum and a decanter is employed to separate the aqueous product from the organic reflux. For esterification reactions, propyl acetate, butyl acetate, butyl propionate, and amyl acetate are good examples of this type of reactive distillation, because they all share the following characteristics: (1) a large two phase zone exists, (2) the minimum boiling azeotrope is located in the two-phase zone, and (3) one end of all tie lines points to the product (typically water). Since phase split description and location of the minimum boiling azeotropre are crucial for correct process description, the selection of thermodynamic models and corresponding binary parameters become important. Unlike typical two-phase systems, the model should be able to describe VLLE behavior as well as to locate all azeotropes. In an amyl acetate case study, the results clearly indicate that erroneous process designs may result if the thermodynamic model fails to capture the azeotropes or to locate two-phase zone. Next, a specific chemical system: butyl propionate esterification process is studied. Following the approach of Kuo (2001), a systematic procedure is employed for the design of butyl propionate heterogeneous reactive distillation. Again, significant energy saving can be achieved by appropriate feed trays arrangement and the total annual cost (TAC) is minimized by finding the optimal number of reactive trays. Then, the issue control structure design for heterogeneous reactive distillation is studied. They design procedure consists of the following steps: (1) set control objective, (2) selection of controlled variables, (3) determine controller structure, and (4) find controller settings. Since the top product composition is determined by the tie lines, intuitively, we are dealing with a single-input-single-output (SISO) system. Unfortunately, as pointed out by Luyben (2000), an internal composition has to be controlled in order to achieve material balance. Therefore, we have, at least, a 2 2 control problem. The relative gain array (RGA) is used to characterize the interaction and determine corresponding controller structure and to provide variable pairing if decentralized controllers are preferred. The relay feedback autotuning is employed to find controller parameters. As for temperature control, the non-square relative gain (NRG) is used to find temperature control tray and, generally, it results in an almost one-way decoupled system. Therefore, decentralized PI controllers are employed. Since offsets in product composition may result in temperature control, feedforward compensation can also be devised to keep the compositions close to their set points. The turn-down problem is explored next. A well designed heterogeneous reactive distillation column may become over-capacity when the production rate is decreased and this can lead to severe operation problem as the two-liquid phase begins to appear on the trays. On the other hand, we have used up all possible manipulated variables. An approach is proposed to overcome the turn-down problem: splitting the lower section (1-butanol) feed to a lower feed location. That is to lower the reaction capability of the reaction zone by moving the light reactant feed to a lower section. This control system over-design provides the flexibility to handle production rate changes in reactive distillation. Results show the effective control can be achieved using the proposed procedure.

目錄
中文摘要 I
英文摘要 III
誌謝 VI
目錄 VII
圖索引 X
表索引 XIV
第一章 緒論 1
1.1 簡介………………………………………………1
1.2 論文組織…………………………………………3
第二章 熱力學模式和VLLE 4
2.1 異相之定義……………………………………… 4
2.2 熱力學模式……………………………………… 6
2.3 VLLE……………………………………………… 8
2.3.1 其它七組之VLLE…………………………..…..9
2.4 製程設計……………………………………… .10
2.4.1 塔頂有分相槽之設計……………………10
2.4.2 塔頂無分相槽之設計……………………11
2.5 結果與討論……………………………………..12
第三章 異相反應蒸餾系統 23
3.1 丙酸丁酯的熱力模式…………………………23
3.1.1 液相所使用熱力學模式………………..24
3.1.2 氣相所使用熱力學模式………………..24
3.1.3 剩餘曲線圖……………………………….25
3.1.4 兩相區之探討…………………………….28
3.1.5 座標轉換系統…………………………….29
3.2 丙酸丁酯的動力學模式………………………30
第四章 穩態設計 39
4.1 程序描述………………………………………..39
4.2 設計步驟………………………………………..39
4.3 最適化設計之結果…………………………….41
4.4 最適化設計之探討…………………………….49
4.4.1 組成分布…………………………………..49
4.4.2 溫度分布…………………………………..50
4.4.3 蒸餾線……………………………………..50
第五章 控制系統設計 64
5.1 控制環路設計…………………………………..64
5.2濃度控制…………………………………………65
5.2.1 控制器參數調諧………………………….67
5.2.2 動態模擬結果…………………………….68
5.2.3 進料二股流量減少20%之探討………..69
5.2.4 濃度控制(修正後)……………………….70
5.3溫度控制…………………………………………71
5.3.1 溫度量測點選擇………………………….72
5.3.2 控制器參數調諧………………………….76
5.3.3 動態模擬結果…………………………….77
5.3.4 溫度控制(修正後)……………………….78
5.4 溫度控制(前饋控制)………………………….78
第六章 結論 98
參考文獻 99
附錄A 105
作者簡介 107
圖索引
2-1 二成分系統在一大氣壓下之氣液平衡曲線：（a）水－乙酸戊酯（b）水－乙酸（c）乙酸－乙酸戊酯（d）水－正戊醇（e）正戊醇－乙酸戊酯（f）乙酸－正戊醇……………………………………………….15
2-2 三成分系統之剩餘曲線及液液平衡曲線圖：（a）水－乙酸－乙酸戊酯（b）水─乙酸－正戊醇（c）乙酸－正戊醇─乙酸戊酯（d）水－正戊醇－乙酸戊酯……………….16
2-3 乙酸戊酯的三成分之兩相區分布圖………17
2-4 在一大氣壓，25℃下二成分氣液平衡曲線圖：(1)~(8)為表2.2的八組不同NRTL model參數所得的氣液平衡圖，分別為水─乙酸戊酯、水─正戊醇………………………………..18
2-5 (1)~(8)為表2.2的八組不同NRTL model參數所得的水─正戊醇─乙酸戊酯之剩餘曲線及液液平衡曲線圖……………………………20
2-6 (1)~(8)為表2.2的八組不同NRTL model參數所得的三成分之兩相區分布圖…………….21
2-7 乙酸戊酯製程圖：(A)塔頂有加裝分相槽(B)塔頂無加裝分相槽……………………………22
3-1 乙酸、正戊醇、乙酸戊酯之剩餘曲線圖(RCM)。○代表Unstable node(如點A、B)，●代表Stable node(如點C、D)，□代表Saddle(如點E)……………...……..…….…..32
3-2 二成分系統在一大氣壓下之氣液平衡曲線：（a）水－丙酸丁酯（b）水－丙酸（c）丙酸－丙酸丁酯（d）水－正丁醇（e）正丁醇－丙酸丁酯（f）正丁醇－丙酸…………..33
3-3 三成分系統之剩餘曲線及液液平衡曲線圖：(a) 丙酸-正丁醇-丙酸丁酯，(b) 水-丙酸-丙酸丁酯，(c) 水-正丁醇-丙酸丁酯，(d) 水-丙酸-正丁醇……………………………….34
3-4 丙酸丁酯的三成分之兩相區分布圖………35
3-5 丙酸丁酯四成分系統的三維(3D)兩相區圖…………………………………………………36
3-6 四成分系統由三維空間(3D)到二維空間(2D)的座標轉換過程。(a)座標投射，(b)二維座標圖……………………………………………..37
3-7 丙酸丁酯四成分系統的二維(2D)兩相區圖…………………………………………………38
4-1 丙酸丁酯製程圖………………………………52
4-2 反應板5板之設備成本、操作成本及年總成本(TAC)………………………………………….53
4-3 反應板6板之設備成本、操作成本及年總成本(TAC)………………………………………….53
4-4 反應板7板之設備成本、操作成本及年總成本(TAC)………………………………………….54
4-5 不同反應板之設備成本、操作成本及年總成本(TAC)………………………………………….54
4-6 表4.1的case1 (NR/Nrxn/NS=1/4/12)之組成及各板反應分率分布………………………………55
4-7 表4.1的case2 (NR/Nrxn/NS=1/5/12)之組成及各板反應分率分布………………………………55
4-8 表4.1的case3 (NR/Nrxn/NS=1/6/12)之組成及各板反應分率分布………………………………56
4-9 表4.1的case4 (NR/Nrxn/NS=1/7/12)之組成及各板反應分率分布………………………………56
4-10 表4.1的case1 (NR/Nrxn/NS=1/4/12)之溫度分布…………………………………………………57
4-11 表4.1的case2 (NR/Nrxn/NS=1/5/12)之溫度分布…………………………………………………57
4-12 表4.1的case3 (NR/Nrxn/NS=1/6/12)之溫度分布…………………………………………………58
4-13 表4.1的case4 (NR/Nrxn/NS=1/7/12)之溫度分布…………………………………………………58
4-14 NR/Nrxn/NS=1/5/12，NF1=13~17，NF2=17的組成分布、各板反應分率分布及溫度分布….59
4-15 反應板5板，改變進料位置之設備成本、操作成本及年總成本(TAC)…………………….60
4-16 反應板6板，改變進料位置之設備成本、操作成本及年總成本(TAC)…………………….60
4-17 反應板7板，改變進料位置之設備成本、操作成本及年總成本(TAC)…………………….61
4-18 不同反應板數(Nrxn=5、6、7)，取最佳近料位置後之設備成本、操作成本、觸媒成本及年總成本(TAC)……………………………………61
4-19 表4.4的case1 (NR/Nrxn/NS=1/5/12，NF1/NF2=15/17)之組成及各板反應分率分布…………………………………………………62
4-20 表4.4的case1 (NR/Nrxn/NS=1/5/12，NF1/NF2=15/17)之溫度分布…………………62
4-21 表4.4的case1 (NR/Nrxn/NS=1/5/12，NF1/NF2=15/17)的蒸餾曲線，其中F1為正丁醇進料位置，F2為丙酸進料位置，NT為冷凝器位置，Daq為塔頂的水相，Dorg為塔頂的有機相，□代表液相組成，△代表氣相組成或塔頂全冷凝後的液相組成，○代表穿過二相區曲面的點………………………………….63
5-1 丙酸丁酯反應蒸餾塔濃度控制架構圖……80
5-2 雙環路閉環測試結果…………………………81
5-3 濃度控制－進料二股流量正10%干擾測試…………………………………………………82
5-4 濃度控制－進料二股流量正20%干擾測試…………………………………………………82
5-5 濃度控制－進料二股流量比例正負2%干擾測試………………………………………………83
5-6 濃度控制－進料二股流量比例正負5%干擾測試………………………………………………83
5-7 在濃度控制系統下，進料二股流量減少20%時，塔頂的氣相(yNT)及液相(xNT)組成分布：(A)Original Control，(B)Modified Control……………..84
5-8 丙酸丁酯反應蒸餾塔濃度控制架構圖(修正後)………………………………………………..85
5-9 濃度控制(修正後)－進料二股流量正負10%干擾測試………………………………………..86
5-10 濃度控制(修正後)－進料二股流量正負20%干擾測試………………………………………..86
5-11 在濃度控制(修正後)系統下，塔頂的氣相(yNT)及液相(xNT)組成分布………………………….87
5-12 丙酸丁酯反應蒸餾塔溫度控制架構圖…..88
5-13 再沸器熱負載(QR)正負1%之靈敏度測試分析…………………………………………………89
5-14 進料二股流量比例(FBuOH/FHOPr)正負1%之靈敏度測試分析…………………………………….89
5-15 再沸器熱負載(QR)正負2%之靈敏度測試分析…………………………………………………90
5-16 進料二股流量比例(FBuOH/FHOPr)正負2%之靈敏度測試分析…………………………………….90
5-17 T4和T16的溫度控制－進料二股流量正10%干擾測試………………………………………..91
5-18 T4和T16的溫度控制－進料二股流量正20%干擾測試………………………………………..91
5-19 T4和T16的溫度控制－進料二股流量比例正負2%干擾測試…………………………………92
5-20 T4和T16的溫度控制－進料二股流量比例正負5%干擾測試…………………………………92
5-21 丙酸丁酯反應蒸餾塔溫度控制架構圖(修正後)………………………………………………93
5-22 T4和T16的溫度控制(修正後)－進料二股流量正負10%干擾測試…………………………….94
5-23 T4和T16的溫度控制(修正後)－進料二股流量正負20%干擾測試…………………………….94
5-24 濃度控制系統中，進料二股流量的變化對第4板溫度(T4)及第16板溫度(T16)的影響……95
5-25 丙酸丁酯反應蒸餾塔溫度控制架構圖(前饋控制)…………………………………………….96
5-26 T4和T16的溫度控制(前饋控制)－進料二股流量正負10%干擾測試…………………………97
5-27 T4和T16的溫度控制(前饋控制)－進料二股流量正負20%干擾測試…………………………97
表索引
2-1 目前以反應蒸餾程序生產是否有加裝分相槽的製程…………………..…………………….5
2-2 NRTL Model for the Acetic acid(1) /1-Pentanol(2) /Amyl acetate(3) / Water(4)………………………………..6
2-3 不同NRTL參數的共沸現象之列表………….8
2-4 利用(表2.2)八組NRTL參數的反應蒸餾塔之操作成本及設備成本和TAC值列表…..14
3-1 丙酸、正丁醇、水及丙酸丁酯之物性列表…………………………………………………23
3-2 NRTL model參數值列表………………………..24
3-3 氣相所使用之維里係數參數列表…………25
3-4 不同成分組成所具有的共沸現象之列表..27
3-5 三成分RCM中node(節點)及saddle(鞍點)數目…………………………………………………28
3-6 非理想溶液之Q-H Model的動力式參數……31
4-1 不同反應板數的反應蒸餾塔之操作成本及設備成本和TAC值列表………………………43
4-2 NR/Nrxn/NS=1/5/12，改變進料板結果…………44
4-3 改變進料位置-反應板6、7板……………….46
4-4 不同進料板的反應蒸餾塔之操作成本及設備成本和TAC值列表…………………………48
4-5 反應蒸餾塔中塔底、正丁醇進料、丙酸進料、泠凝器液相、氣相及塔頂水相、有機相的組成…………………………………………..51
5-1 濃度控制器參數列表………………………..68
5-2 NRG分析結果…………………………………..74
5-3 溫度控制器參數………………………………76

參考文獻
[中文]
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[英文]
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