隨著石化燃料的廣泛應用，全球二氧化碳濃度不斷升高，使得二氧化碳有關的研究愈來愈被重視，二氧化碳捕獲和儲存(CCS)一直被視為是減少碳排放、減緩溫室效應的重要途徑。雖然在捕獲方面一直有很大的進展，但是儲存技術方面卻停滯不前。因此如何減少碳排放及如何利用二氧化碳轉換成化學及能源產品成為了被大家十分重視的問題。現今，雖然已經有很多二氧化碳再利用的製程被提出了，但在考慮反應消耗的能量和排放的二氧化碳後，是否還能有減碳的效果?
本研究利用了 GH-space 來進行分析，GH-space 是一種理想化的簡單分析方法，只需要各反應的反應熱、反應自由能以及反應條件即可透過熱力學的計算得到最理想的製程能耗，可以快速地進行分析，研究中，分析了幾種二氧化碳再利用的製程，第一部份是不同重組反應生產不同比例合成氣的減碳效果分析，和幾種以合成氣為原料的製程分析(甲醇、丁醛)，第二部份則是碳酸二甲酯的製程分析，目的是找出最佳的碳酸二甲酯合成反應路徑。
第一部份的結果中，甲烷的不同重組反應分析顯示，二元重組(乾式重組+水蒸氣重組)在生產氫碳比 1.6 以下的合成氣時才有減碳效果，而三元重組(乾式重組+水蒸氣重組+甲烷部分氧化)則是在生產氫碳比 2.2 以下的合成氣時就有減碳效果，最後使用綠能氫的組合(乾式重組+綠能氫)則是在生產任何比例的合成氣時皆有減碳效果，但使用綠能氫的組合相較於其他兩者有著原料價格較貴的缺點。在甲醇的製程研究中也顯示了分析結果跟 Aspen plus 的模擬結果差不多。
第二部份在不同路徑合成碳酸二甲酯的研究中可以發現，用 GH-space 分析找出最佳路徑是可行的，只以減碳量來看，酯交換法、直接合成法、以環氧丁烷脫水的直接合成法皆有很好的減碳量，而甲醇氧化羰基化法則有著最差的減碳量，若是綜和減碳量、反應容易進行程度和產品利潤方面，經由碳酸丙烯酯的尿素間接醇解法減碳量不低、也沒有轉化率差的問題，應可以說是一條較好的路徑。

With the increasing use of fossil fuels and the increasing concentration of carbon dioxide in the world. Carbon dioxide capture and storage (CCS) has been regarded as an important way to reduce carbon emissions. Although the considerable progress has been made in capturing, storage technology has been stagnant. So how to reduce carbon emissions and how to transform carbon dioxide into chemical and energy products has become a very important issue.
In this study, GH-space idealized process analysis was used to analyze several carbon dioxide reusing processes. This ideal analysis was used to calculate the least energy-consuming and to minimize the carbon dioxide emissions from the process.
The research is divided into two parts. Frist part is to study the carbon reduction ability of different H2/CO ratio of syngas produced by different reforming reactions. Second part is to find the best reaction path to synthesis DMC from CO2 and methanol.
For the syngas synthesis research, we found Dry/Steam process has ability to reduce CO2 if H2/CO ratio less than 1.6. Dry/Steam/Partial process can reduce CO2 when H2/CO ratio less than 2.2. Dry+H2 process can reduce CO2 in any H2/CO ratio. In raw material cost research shows, only if H2 price lower than 1000 USD/Ton, Dry/H2 process can compete with the others.
For the DMC synthesis research, we found it is possible to find the best reaction path by GH-space. In terms of carbon reduction ability. Transesterification method, direct synthesis method and direct synthesis method (with BO dehydration) all have very good carbon reduction ability, and methanol oxidation carbonylation method has the worst carbon reduction ability. If consider all carbon reduction ability, reaction conversion and product profits. Urea indirect alcoholysis via PC should be the best path.

目錄
摘要............................................................................................................................ I
ABSTRACT ................................................................................................................. II
目錄.......................................................................................................................... III
圖目錄...................................................................................................................... VI
表目錄...................................................................................................................... IX
第一章、緒論............................................................................................................ 1
1.1 研究背景......................................................................................................... 1
1.2 研究動機......................................................................................................... 1
第二章、文獻回顧.................................................................................................... 3
2.1 GH-space 介紹................................................................................................. 3
2.2 甲烷重組反應生產合成氣的製程介紹......................................................... 5
2.2.1 乾式重組反應.......................................................................................... 5
2.2.2 水蒸氣重組反應...................................................................................... 6
2.2.3 部分氧化反應.......................................................................................... 6
2.2.4 二元和三元重組製程.............................................................................. 7
2.2.5 以合成氣為原料的製程.......................................................................... 8
2.3 碳酸二甲酯及其合成方法介紹..................................................................... 9
2.3.1 碳酸二甲酯介紹...................................................................................... 9
2.3.2 二氧化碳直接合成法.............................................................................. 9
2.3.3 酯交換法................................................................................................ 10
2.3.4 尿素直接醇解法.................................................................................... 11
2.3.5 尿素間接醇解法.................................................................................... 11
2.3.6 甲醇氧化羰基化法................................................................................ 12
2.3.7 二氧化碳直接合成法 (以 BO 脫水) ................................................... 13
第三章、研究方法.................................................................................................. 15
3.1 熱力學參數................................................................................................... 15
3.2 GH-space 分析............................................................................................... 16
3.2.1 決定初步反應流程圖............................................................................ 16
3.2.2 反應溫度修正........................................................................................ 18
3.2.3 反應壓力修正........................................................................................ 20
3.2.4 混和與分離的影響................................................................................ 21
3.3 二氧化碳排放............................................................................................... 22
第四章、GH-SPACE 分析結果 ................................................................................ 23
4.1 甲烷重組反應產生不同 H2/CO 合成氣的研究 .......................................... 23
4.1.1 乾式重組/水蒸氣重組組合 .................................................................. 23
4.1.2 乾式重組/部分氧化組合 ...................................................................... 26
4.1.3 部分氧化/水蒸氣重組組合 .................................................................. 26
4.1.4 乾式重組/綠能氫組合 .......................................................................... 27
4.1.5 減碳量結果比較.................................................................................... 28
4.1.6 原料成本................................................................................................ 29
4.2 以合成氣為原料的產品分析 (甲醇製程) .................................................. 30
4.2.1 乾式重組製程 (進料組成: 𝑪𝑯𝟒 + 𝑪𝑶𝟐 + 𝑯𝟐) ................................. 30
4.2.2 部分氧化製程 (進料組成: 𝑪𝑯𝟒 + 𝑶𝟐) .............................................. 32
4.2.3 雙重組製程 (進料組成: 𝑪𝑯𝟒 + 𝑪𝑶𝟐 + 𝑯𝟐𝑶) .................................. 33
4.2.4 各甲醇製程比較.................................................................................... 35
4.3 以合成氣為原料的產品分析 (丁醇製程) .................................................. 37
4.3.1 丁醛的合成............................................................................................ 37
4.3.2 丁醇的合成............................................................................................ 38
4.4 碳酸二甲酯................................................................................................... 41
4.4.1 二氧化碳直接合成法............................................................................ 41
4.4.2 酯交換法................................................................................................ 42
4.4.3 尿素直接醇解法.................................................................................... 44
4.4.4 尿素間接醇解法 (via EC) .................................................................... 46
4.4.5 尿素間接醇解法 (via PC) .................................................................... 48
4.4.6 甲醇氧化羰基化法................................................................................ 50
4.4.7 二氧化碳直接合成法 (以 BO 脫水) ................................................... 53
4.4.8 七種利用二氧化碳製備碳酸二甲酯製程的比較................................ 55
第五章、結論.............................................................................................. 58
符號說明.................................................................................................. 59
參考文獻.................................................................................................. 60

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