因應溫室氣體的排放減量與能源效率的提升，氫氣能源莫不受到工業國家的青睞與重視，配合「氫能」燃料電池的設計與發展可說是現代的顯學。「乙醛」是作為合成各種樹脂、中間體的中間原料，製程中尚可回收重要的氫氣。
  本論文，針對兩個製程進行研究：「氫能程序」與「乙醛製程」。論文中主要使用兩套程序軟體：AspenPlus進行製程設計與模擬，SuperTarget進行狹點分析和換熱器網路合成，有效完成研究方案的熱能整合。

To deal with the emission reduction of greenhouse gases and the improvement of energy efficiency, hydrogen energy has been attracted by the industrialized countries.  As a result, the use of hydrogen in the design and development of fuel cells has become an important research issue today.  On the other hand, acetaldehyde has been an important intermediate chemicals in the petrochemical industries.  Additionally, this process is able to recover the precious hydrogen for use in the fuel cells.
  In this thesis, we have successfully carried out two case studies: one is the “hydrogen process”, and the other is the “acetaldehyde process.”  Two software were utilized in the research – AspenPlus and SuperTarget.  The former was used for the process synthesis, design, and simulation; the latter was used to carry out the pinch analysis and the synthesis of heat exchanger network.

目錄
誌謝 .....................................................i
中文摘要 ................................................ii
英文摘要 ...............................................iii
目錄  ...................................................iv
圖目錄  .................................................vi
表目錄 ...................................................x
第一章  諸論 .............................................1
1.1  研究動機.............................................1
1.2  研究目的與方法.......................................1
第二章 理論基礎...........................................2
2.1  狹點技術在能源節約上之應用...........................2
2.1.1  製程模擬...........................................3
2.1.2  狹點分析原理.......................................5
2.1.3  換熱器網路合成 ...................................17
第三章  氫能程序之熱能整合...............................22
3.1前言 .................................................22
3.1.1 研究方法...........................................26
3.1.2 進行步驟...........................................28
3.1.3 程序合成與設計.....................................28
3.2 蒸汽重組.............................................30
3.2.1 蒸氣重組爐反應式...................................30
3.3 製程分析與模擬.......................................31
3.3.1 製程描述...........................................31
3.3.2 模擬結果...........................................31
3.3.3 熱能整合應用.......................................39
3.3.4 換熱器網路之合成...................................49
3.4 變壓吸附.............................................65
3.4.1  PSA的基本原理.....................................65
3.4.2 變壓吸附之數學模式.................................66
3.4.3 SOFC發電系統之整合設計.............................68
3.5 SOFC發電系統之結果與討論.............................70
3.5.1 一氧化碳 (CO) 的問題...............................70
3.5.2 電力計算...........................................73
3.5.3 不同烷烴與蒸汽之重組產物分析.......................77
第四章  乙醇脫氫製造乙醛程序之熱能整合研究...............92
4.1 前言.................................................92
4.2 製程描述.............................................93
4.3 進行步驟.............................................95
4.4 製程模擬.............................................96
4.5 狹點技術在乙醛製程上之應用..........................103
4.5.1 數據擷取..........................................103
4.5.2 狹點分析..........................................103
4.5.3 換熱器網路之合成..................................118
第五章  結論與建議......................................144
符號說明................................................145
參考文獻................................................147

圖目錄

圖2.1  複合曲線預測能源目標...............................7
圖2.2  換熱系統的熱源與熱沼特性...........................7
圖2.3  狹點分解(零越過狹點熱流)...........................7
圖2.4  狹點分解(越過狹點XP單位的熱流).....................7
圖2.5  簡例製程流程圖....................................10
圖2.6  熱交換器E-101之T-Q圖..............................11
圖2.7  熱交換器E-103之T-Q圖..............................11
圖2.8  熱交換器E-102熱物流之T-Q圖........................11
圖2.9  熱交換器E-102冷物流之T-Q圖........................11
圖2.10 蒸餾塔T-101冷凝器之T-Q圖..........................12
圖2.11 蒸餾塔T-101再沸器之T-Q圖..........................12
圖2.12 T-Q圖之線性分段...................................13
圖2.13 熱交換器E-103之熱物流T-Q圖........................14
圖2.14 蒸餾塔冷凝器之熱物流T-Q圖.........................14
圖2.15 熱物流複合曲線圖..................................14
圖2.16  冷物流複合曲線圖.................................15
圖2.17  最小趨近溫度5℃的總冷熱複合曲線圖................15
圖2.18  △Tmin=5℃時之換熱器網格圖.......................16
圖2.19  △Tmin=5℃完成換熱器網路合成之網格圖.............19
圖2.20  △Tmin=5℃完成換熱器網路合成之最後組態設計圖.....21
圖3.1  氫氣為燃料之兩極式SOFC示意圖......................25
圖3.2  氫能應用之大型發電整合設計之方塊流程圖............27
圖3.3  氫能/燃料電池程序流程圖...........................29
圖3.4  AspenPlus之氫能程序(Unit 100+Unit 200)流程圖......33
圖3.5  AspenPlus之燃料電池程序(Unit 300)流程圖...........36
圖3.6  AspenPlus之氫能/燃料電池程序流程圖................38
圖3.7  PSA出口之氫氣之換熱器E-201之T-Q圖.................40
圖3.8  重組後出口之換熱器E-202之T-Q圖....................40
圖3.9  換熱器E-203之T-Q圖................................41
圖3.10  PSA入口之換熱器E-204之T-Q圖......................41
圖3.11  迴流之換熱器E-205之T-Q圖.........................42
圖3.12  加熱爐F-101 溫度對焓的關係圖.....................42
圖3.13  最小趨近溫度T=5℃時，氫能/燃料電池程序之總冷熱複合曲線圖...................................................43
圖3.14  最小趨近溫度T=10℃時，氫能/燃料電池程序之總冷熱複合曲線圖...................................................44
圖3.15  最小趨近溫度T=15℃時，氫能/燃料電池程序之總冷熱複合曲線圖...................................................45
圖3.16  最小趨近溫度T=20℃時，氫能/燃料電池程序之總冷熱複合曲線圖...................................................46
圖3.17  最小趨近溫度T=25℃時，氫能/燃料電池程序之總冷熱複合曲線圖...................................................47
圖3.18  △Tmin=5℃ 氫能/燃料電池程序之網路合成網格圖.....50
圖3.19  △Tmin=10℃ 氫能/燃料電池程序之網路合成網格圖....52
圖3.20  △Tmin=15℃ 氫能/燃料電池程序之網路合成網格圖....55
圖3.21  △Tmin=20℃ 氫能/燃料電池程序之網路合成網格圖....59
圖3.22  △Tmin=25℃ 氫能/燃料電池程序之網路合成網格圖....63
圖3.23  氫能/燃料電池程序在△Tmin=15℃之最後組態設計圖...69
圖3.24  合成氣反應成甲醇之流程圖.........................72
圖3.25  甲烷和一氧化碳反應成醋酸之流程圖.................72
圖3.26  不同烷烴與蒸汽在重組爐內之模擬...................77
圖3.27  甲烷的重組爐溫度變化示意圖.......................78
圖3.28  甲烷之水蒸氣進量變化示意圖.......................79
圖3.29  乙烷的重組爐溫度變化示意圖.......................80
圖3.30  乙烷之水蒸氣進量變化示意圖.......................81
圖3.31  丙烷的重組爐溫度變化示意圖.......................82
圖3.32  丙烷的水蒸氣進量變化示意圖.......................83
圖3.33  丁烷的重組爐溫度變化示意圖.......................84
圖3.34  丁烷的水蒸氣進量變化示意圖.......................85
圖3.35  戊烷的重組爐溫度變化示意圖.......................86
圖3.36  戊烷的水蒸氣進量變化示意圖.......................87
圖3.37  甲、乙、丙、丁、戊烷混合的重組爐溫度變化示意圖...88
圖3.38  甲、乙、丙、丁、戊烷混合之水蒸氣變化示意圖.......89
圖4.1  乙醇脫氫製程之PFD圖...............................94
圖4.2  AspenPlus之乙醇脫氫製程流程圖.....................97
圖4.3  乙醇進料之換熱器E-101之T-Q圖.....................104
圖4.4  乙醇進料之換熱器E-102之T-Q圖.....................104
圖4.5  反應器R-101 出口冷凝器E-103之T-Q圖...............105
圖4.6  反應器R-101 出口冷凝器E-104之T-Q圖...............105
圖4.7  驟沸槽V-101 出口換熱器E-105之T-Q圖...............106
圖4.8  蒸餾塔T-201冷凝器之T-Q圖.........................107
圖4.9  蒸餾塔T-201再沸器之T-Q圖.........................107
圖4.10  蒸餾塔T-202冷凝器之T-Q圖........................108
圖4.11  蒸餾塔T-202再沸器之T-Q圖........................108
圖4.12  蒸餾塔T-203冷凝器之T-Q圖........................109
圖4.13  蒸餾塔T-203再沸器之T-Q圖........................109
圖4.14  蒸餾塔T-204冷凝器之T-Q圖........................110
圖4.15  蒸餾塔T-204再沸器之T-Q圖........................110
圖4.16  △Tmin=5℃時，乙醇脫氫製程之複合曲線圖..........112
圖4.17  △Tmin=10℃時，乙醇脫氫程序之複合曲線圖.........113
圖4.18  △Tmin=15℃時，乙醇脫氫程序之複合曲線圖.........114
圖4.19  △Tmin=20℃時，乙醇脫氫程序之複合曲線圖.........115
圖4.20  △Tmin=25℃時，乙醇脫氫程序之複合曲線圖.........116
圖4.21  乙醇脫氫製程△Tmin=5℃之換熱器網路合成之網格圖..121
圖4.22  乙醇脫氫製程△Tmin=10℃之換熱器網路合成之網格圖.126
圖4.23  乙醇脫氫製程△Tmin=15℃之換熱器網路合成之網格圖.131
圖4.24  乙醇脫氫製程△Tmin=20℃之換熱器網路合成之網格圖.136
圖4.25  乙醇脫氫製程△Tmin=25℃之換熱器網路合成之網格圖.141
圖4.26  乙醇脫氫製程△Tmin =10℃時之最後組態設計圖......143

表目錄

表2.1  簡例之物質資料表...................................8
表2.2  換熱器網路配對資料表..............................20
表3.1  氫能/燃料電池程序之物流資料表.....................34
表3.2  燃料電池物流表....................................37
表3.3  冷、熱物流資料表..................................39
表3.4  不同最小趨近溫度之冷、熱公用設施比較..............48
表3.5  △Tmin=15℃之氫能/燃料電池程序換熱器網路配對資料表56
表3.6  △Tmin=20℃之氫能/燃料電池程序換熱器網路配對資料表60
表3.7  △Tmin=25℃之氫能/燃料電池程序換熱器網路配對資料..64
表3.8  PSA Unit 之閥的開閉狀態表.........................68
表3.9  模擬甲烷與水蒸汽比例重組後之物流表................91
表4.1  乙醇脫氫製程之物流資料表..........................98
表4.2  乙醇脫氫製程之熱交換器資料表.....................101
表4.3  乙醇脫氫製程之物流表.............................111
表4.4  乙醇脫氫製程之不同最小趨近溫度之比較表...........117
表4.5  △Tmin=5℃之換熱器網路配對資料表.................122
表4.6  △Tmin=10℃之換熱器網路配對資料表................127
表4.7  △Tmin=15℃之換熱器網路配對資料表................132
表4.8  △Tmin=20℃之換熱器網路配對資料表................137
表4.9  △Tmin=25℃之換熱器網路配對資料表................142

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