臺灣博碩士論文加值系統

本研究旨在探討各類煤炭氣化以多聯產製化學品的製程設計、最適化與經濟評估研究。由於國內缺少能源來源，因此逾98%的能源來源仰賴進口。而煤炭價格便宜、全球存量豐、且易於運送，因此為國內最主要的能源來源之一，未來煤炭在國內仍將扮演重要的角色。
氣化過程為此類研究的核心，而本研究以此為起點。首先，本研究提出一維的氣化爐模型，探討煤炭與生質能源在不同條件下的操作情形。接續探討的是煤炭氣化以合成天然氣生產程序、以及合成天然氣與氨的多聯產生產與操作。由於進口天然氣需要經過壓縮與液化等步驟，導致價格昂貴(11.3~11.7 USD/MMBTU)，因此由煤炭以產合成天然氣頗具經濟效益(10.336 USD/MMBTU)。若以多聯產的方式生產，則可提升經濟效益，但若其中一產物的產量相對過小時，經濟效益的提升即不明顯。
再來探討的是新穎的甲醇產製烯烴程序的整廠製程，以產製乙烯與丙烯產物為主要目標。本研究針對此程序進行完整嚴密的模擬，並仔細探討各個變數所造成的影響。由於丙烷與丙烯沸點相近，不易分離，因此本研究亦特別針對丙烷與丙烯分離系統進行探討。所探討的分離方法有以下四種，分別為使用蒸氣作熱源的傳統單塔分離、使用熱廢水作熱源的傳統單塔式分離、利用蒸氣再壓縮循環做熱整合的傳統單塔式分離、以及利用乙腈溶液作挾帶劑的萃取蒸餾分離。分析結果得知使用熱廢水作熱源的傳統單塔式分離、以及萃取蒸餾分離皆能大幅改善成本以及分離使用的塔板數目。
本文最後探討的合成氣產製乙二醇程序的設計與最適化。此程序包含兩階段，第一階段為將合成氣中一氧化碳轉化為草酸二甲酯，第二階段則將草酸二甲酯氫化成乙二醇。於第一階段中，甲醇於系統中的循環量為最具決定性的變數，其主要由填充床反應器進料中，甲醇與一氧化氮及二氧化氮的總和之莫耳比例(MeOH/NOs)來影響。於第二階段中，最重要的變數為混合進料中氫氣與草酸二甲酯莫爾進料比(HDMR)。
總括而言，本文針對各類煤炭氣化的下游化學品生產程序進行的完整與嚴密的模擬，輔以最適化、熱整合、經濟與能量分析，以仔細探討各程序的內部行為。透過本研究，對於此類程序有了更透徹的了解。

In this work, the design, optimization, and economic evaluation of coal-based poly-generation processes to produce different kind of chemicals are investigated. We lack energy sources in Taiwan, thus over 98% of the energy sources come from importation. Among those energy sources, coal has several advantages such as its relative low proce, abundance, and easy transportation. Therefore, coal has been one of the most important energy sources in Taiwan, and it is expected that its role will be retained in the future.
Gasification is the center of this kind of processes, which is also the starting point of this work. Firstly, a 1-dimension gasifier model is established to investigate the gasification performance of coal or biomass under different operating conditions. After that, the coal-to-synthetic natural gas (SNG) and coal-based poly-generation process to produce SNG and ammonia are followed. Because importation of natural gas required liquefaction and compression, thus the importation price is quite expensive in Taiwan (11.3~11.7 USD/MMBTU). Thus, converting coal into SNG can be economically attractive (10.336 USD/MMBTU). If the poly-generation configuration is adopted, the economic performance can be further enhanced. But the enhancement of economic performance may be not obvious once one of the product flowrate is too small.
The next topic to investigate is the novel methanol-to-olefin (MTO) process, and the main products are ethylene and propylene. In this work, the rigorous simulation of this process is studied, and the influences from variables are carefully investigated. Besides, due to the close boiling point between propylene and propane, separating them through distillation is not easy. Thus, four method for separation propane with propylene are studied. They are traditional single-column separation using steam as the heat source (case 1), using waste hot water as the heat source (case 2), distillation with the vapor recompression cycle (case 3), and the extractive distillation using acetonitrile solution as the entrainer (case 4). From the results, it is found that case 2 and case 4 may be economically attractive.
The final topic is the syngas-to-ethylene glycol (EG) process. There are two stages in this process. In the first stage, CO in syngas is converted into dimethyl oxalate (DMO) as an intermediate, while in the second stage, DMO is hydrogenated to become EG. In the first stage, the circulation rate of methanol inside the process is the most important one. It is mainly determined by the ratio of methanol to the combined nitric oxide and nitric dioxide flowrate into the packed-bed reactor. In the second stage, the most influential variable is the molar ratio of hydrogen and DMO in the combined feed.
In short, many coal-based poly-generation processes for producing chemicals are rigorously studied in this work. The analysis methods include optimization, heat integration, economic and energetic evaluation. Through this work, a better understanding toward these processes can be obtained.

口試委員會審定書 i
誌謝 iii
中文摘要 v
英文摘要 vii
目錄 xi
圖目錄 xv
表目錄 xix
第一章 緒論 1
1-1 研究背景與動機 1
1-2文獻探討 5
1-2.1 燃料氣化產製合成氣 5
1-2.2 淨煤相關策略 7
1-2.3 合成氣處理 8
1-2.4 合成氣於下游化學廠的多聯產製程 10
1-2.5 合成天然氣製程 12
1-2.6 氨製程 14
1-2.7 烯烴類製程 15
1-2.8 乙二醇製程 19
1-3 組織章節 23
第二章 氣化爐的設計與操作 24
2-1 氣化爐模型設計與驗證 25
2-2 水煤漿氣化之模擬分析 31
2-3 二氧化碳煤漿氣化之模擬分析 34
2-4 煤炭與生質能混摻氣化的模擬分析 36
2-5 結論 38
第三章 煤製合成天然氣程序的設計與經濟分析 39
3-1整廠程序架構 39
3-2空氣分離裝置 41
3-3 合成氣處理段 45
3-3.1酸水氣轉移反應 45
3-3.2 酸氣移除程序 48
3-4 合成天然氣工廠 57
3-5 廢熱回收程序與整廠能量轉換分析 60
3-6 經濟分析 65
3-6.1設備成本 65
3-6.2 固定操作與維修成本: 68
3-6.3變動操作與維修成本: 68
3-6.4經濟結構模型 69
3-6.5經濟分析結果 70
3-7 結論 72
第四章 煤製合成天然氣與氨多聯產程序的設計與經濟分析 73
4-1整廠程序之架構 73
4-2 空氣分離裝置 78
4-3 合成氣潔淨與組成調配 80
4-4 合成天然氣工廠 84
4-5 氨工廠 85
4-6 廢熱回收與再利用 92
4-7 經濟分析 95
4-8 結論 97
第五章、甲醇製烯烴程序的設計與最適化研究 98
5-1 反應段 98
5-2 潔淨段 104
5-3 第一分離段 107
5-4 第二分離段 114
5-5 結論 124
第六章 合成氣製草酸二甲酯程序的設計與最適化研究 125
6-1 反應動力式與反應條件 128
6-1.1 耦聯反應 128
6-1.2 再生反應 130
6-2 整廠程序流程 135
6-3 最適化研究 143
6-3.1 變數歸類與最適化步驟建立 143
6-3.2 最適化結果討論 149
6-4 結論 158
第七章 草酸二甲酯氫化產乙二醇程序的設計與最適化研究 159
7-1氫化反應之動力式與反應條件 161
7-2草酸二甲酯加氫整廠製程 164
7-3製程之最適化研究 168
7-3.1 變數歸類與最適化步驟建立 169
7-3.2 最適化的前置作業 173
7-3.3 完整最適化結果 177
7-4 結論 184
第八章 全文回顧與未來展望 185
參考文獻 188
附錄一、氣化爐中反應計算 200
附錄二、氣化爐中性質計算 204
附錄三、甲醇製烯烴程序反應器能量平衡計算 207
作者簡介 210

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