石腦油裂解後產生約占總質量的15~25%副產品碳五混合物，此混合物富含極具附加價值的原料，包含異戊二烯(IP)、間戊二烯(PD)、環戊烯(CP)和環戊二烯(CPD)等。由於碳五物質的沸點相近且其中有些成分具共沸關係，難以普通的蒸餾方式分離，因此在工業上一般是以燃料燃燒方式處理而未能充分利用。另一普遍使用的方式是將CPD進行二聚反應後產生高沸點的碳十雙環戊二烯(DCPD)，再以蒸餾方式與其它碳五成分進行分離回收，或是利用萃取蒸餾的方式分離高純度的IP。但此程序皆需複雜的反應與蒸餾分離，且採用回流反應物之方式以提高反應轉化率，此亦容易造成整體製程操作上有滾雪球效應，使整廠製程難以控制，因此，整廠製程具有大幅簡化及強化的空間。在傳統碳五分離製程簡化方面，本研究將反應區域由2區簡化至1區，操作單元由8個簡化到6個。此簡化製程可以使整體設備成本大幅降低，並使整廠製程更加容易操作，亦增加產品回收率及濃度，其中，DCPD的濃度從85.00~92.00wt%到至少98.00wt%以上；IP產物維持高濃度(99.75wt%)；PD和CP混和產物濃度也維持在需求89.90wt%以上。在製程強化方面，本研究進一步利用隔牆蒸餾塔和外部熱整合進行強化，使整廠製程的能耗大幅下降。透過模擬結果顯示，此研究改善了現有的碳五分離系統，降低了總成本和操作成本，讓產品擁有更大的附加價值，並使整廠製程在工業上具有更大的兢爭力。

C5 fraction, which accounts for 15-25% in naphtha, consists of molecules such as isoprene (IP), pentadiene (PD), cyclopentene (CP), and cyclopentadiene (CPD) can be used to manufacture petroleum resin and other high value-added products. Yet it is often burned as fuel and not fully utilized because separation of these products with close boiling points is difficult. One common process is to react CPD itself to form high boiling dicyclopentadiene (DCPD) so that it can be separated from the other C5 molecules. In addition, extractive distillation is also used to recover alkynes from light ends. Such a process involves the use of multiple separation columns and reaction zones. Furthermore, it is found that the reactor is highly coupled with one of the separation columns by two recycle streams which may lead to snowball effect and difficulty in control. Hence a wide range of opportunities for process integration and intensification is available. We find that the entire process with reaction and separation can be substantially simplified by reducing the number of reaction zones from 2 to 1 and number of columns from 8 to 6. Such a simplification increases not only process operability but also product concentration of DCPD from a range between 85wt% and 92wt% to at least 98wt%, while maintains the high purity (>99.75 wt %) for the IP stream and specified purity (>89.90 wt %) for the PD plus CP stream. In addition, capital cost can be greatly decreased for the simplified process. This process can be further intensified by using thermal coupling and external heat integration. Much energy saving can be achieved for the intensified process. Simulation results demonstrate that the proposed simplified and intensified process can substantially reduce capital cost, operating cost as well as improve process operability for the separation of a C5 mixture.

摘要 I
Abstract II
目錄 IV
圖目錄 VII
表目錄 1
第一章、緒論 3
1.1 研究背景 3
1.2 研究動機 4
第二章、文獻回顧 5
2.1 現今研究走向 5
2.2精餾雙環戊二烯(DCPD) 6
2.2.1多次二聚解聚以得到雙環戊二烯或環戊二烯 6
2.2.2分離再二聚分離雙環戊二烯 7
2.2.3 DCPD氣相裂解回收DCPD 8
2.2.4氫化DCPD回收其他物質之製程 10
2.3分離異戊二烯(IP) 13
2.3.1乙腈抽提法（ACN法） 13
2.3.2二甲基甲酰胺法（DMF法） 15
2.3.3 N-甲基吡咯烷酮法（NMP法） 15
2.3.4共沸蒸餾，正戊烷 18
2.4 分離間戊二烯(PD) 19
2.4.1精餾分離間戊二烯(PD) 19
2.4.2共沸蒸餾分離間戊二烯(PD) 19
2.5 節能熱整合 21
2.5.1熱耦合設計 21
2.5.2多效熱整合設計 22
2.5.3 HiDiC設計 23
第三章、研究方法 25
3.1 製程目標 25
3.2 熱力學模型 28
3.3 動力學模型 30
3.4 經濟分析 34
第四章、製程簡化與強化 35
4.1 傳統碳五分離製程 35
4.1.1 傳統製程中各塔操作狀況與條件 39
4.2 簡化碳五分離製程 46
4.2.1碳五製程之簡化 48
4.2.1.1二聚反應區之製程簡化 48
4.2.1.2重物質分離區之製程簡化 50
4.2.1.3製程中回流之簡化 50
4.2.2簡化後各塔操作狀況與條件 51
4.2.3 傳統製程和簡化製程比較 56
4.3 隔牆式蒸餾塔系統 57
4.3.1 第一隔牆式蒸餾塔-DWC(1) 58
4.3.2 第二隔牆式蒸餾塔-DWC(2) 60
4.3.3 整合隔牆式蒸餾塔製程 61
4.4 外部熱整合 62
4.4.1 外部熱整合製程設計及結果 63
4.5 全廠製程比較 65
第四章、結論與未來工作 68
附錄A：成本計算公式一覽表 70
附錄B：製程的模擬成果 72
參考文獻 75

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