利用變壓吸附法純化甲烷重組氣得到高純度之氫氣

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姓名

張書鈞(Shu-Jun Zhang) 查詢紙本館藏

畢業系所

化學工程與材料工程學系

論文名稱

利用變壓吸附法純化甲烷重組氣得到高純度之氫氣

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摘要(中)

在全球追求淨零碳排的目標下，尋找新能源成為了一個必然的問題，氫氣的能源重要性是當前的研究議題，但如果要將氫用於燃料電池等用途，則需要極高的純度。
本研究模擬變壓吸附法(pressure swing adsorption, PSA)純化甲烷水蒸氣重組氣(steam methane reforming, SMR)，以活性碳及沸石5A作為吸附劑。甲烷水蒸氣重組氣之氣體組成為75.26%氫氣、22.68%二氧化碳及2.06%一氧化碳，其中沸石5A對於二氧化碳的選擇率較沸石13X更高，且文獻搜尋都是使用活性碳-沸石之雙層吸附劑來做為吸附床，因此本研究使用活性碳-沸石5A雙層吸附劑來探討各程序所獲得之氫氣純度及回收率。
本研究為獲得高純度之氫氣，利用實驗設計(design of experiments, DOE)來找尋符合PSA程序之最適化操作條件，進行多因子兩水準之全因子設計，經由計算所得到之迴歸模型可得到三塔九步驟之結果為氫氣99.12%之純度且回收率為63.08%，及三塔十五步驟之結果為99.999%之純度且回收率為44.19%。
三塔九步驟程序之結果雖氫氣純度只到達99%，只能應用於較基礎之化學反應如石化業、製造氨氣、製造甲醇等，但回收率較三塔十五步驟更佳。
三塔十五步驟程序之結果雖氫氣回收率僅到達44.1981%，但相較三塔九步驟之氫氣純度明顯提升許多，因此此程序能應用在更精密之產業，如燃料電池、半導體產業等。

摘要(英)

Under the global pursuit of the goal of net zero carbon emissions, searching for new energy sources has become an inevitable issue. The energy importance of hydrogen is current research topic, but if hydrogen is to be used in fuel cells or other purposes, extremely high purity is required.
In this study, the simulation of pressure swing adsorption (PSA) was used to purify hydrogen from steam methane reforming gas (SMR) , and activated carbon and zeolite 5A were used as adsorbents.The gas composition of methane steam reforming gas is 75.26% hydrogen, 22.68% carbon dioxide and 2.06% carbon monoxide. Among adsorbents, zeolite 5A has a higher selectivity for carbon dioxide than zeolite 13X, and the literature survey shows activated carbon-zeolite layered adsorbent in adsorption bed is usually used. Therefore, this study uses activated carbon-zeolite 5A layered bed to investigate the hydrogen purity and recovery obtained by PSA.
In order to obtain high-purity hydrogen, this study uses design of experiments (DOE) to find the optimal operating conditions in line with the PSA processes, and conducts a two-level full factorial design. The regression model obtained through calculation can be obtained. The purity of hydrogen by a three-bed nine-step PSA is 99.12% with a recovery of 63.08%, and the purity of hydrogen by a three-bed fifteen-step PSA is 99.999% with a recovery of 44.19%.
As a result of the three-bed nine-step process, although the hydrogen purity reaches only 99%, it can only be applied to relatively basic chemical reactions such as petrochemical industry, ammonia production, methanol production, etc., but the recovery is better than the three-bed fifteen-step procedure.
Although the hydrogen recovery of the three-bed fifteen-step procedure is only 44.1981%, the hydrogen purity is significantly improved compared to the three-bed nine-step process. Therefore, this process can be applied to more sophisticated industries, such as fuel cells and semiconductor industries.

關鍵字(中)

★ 變壓吸附
★ 氫氣純化

關鍵字(英)

★ Pressure Swing Adsorption
★ Hydrogen Purification

論文目次

摘要 I
ABSTRACT II
誌謝 IV
目錄 V
圖目錄 VIII
表目錄 X
第一章緒論 1
第二章簡介及文獻回顧 3
2-1 吸附簡介 3
2-1-1 吸附基本原理 3
2-1-2 吸附劑與選擇率 4
2-1-3 物理吸附程序比較 6
2-1-4 突破曲線 8
2-2 變壓吸附程序 10
2-2-1 PSA程序起源及後續發展改進 10
2-2-2 理論回顧 14
2-3 文獻回顧 16
第三章假設及理論 19
3-1 基本假設 19
3-2 統制方程式 20
3-3 吸附平衡關係式 24
3-3-1 等溫吸附平衡關係式 24
3-3-2 質傳驅動力模式(Driving force model) 25
3-3-3 吸附熱關係式 25
3-4 參數推導 26
3-4-1 軸向分散係數(Axial dispersion coefficient) 26
3-4-2 熱傳係數 28
3-4-3 線性驅動力質傳係數 30
3-5 邊界條件與流速 32
3-5-1 邊界條件與節點流速 32
3-5-2 閥公式 33
3-6 求解步驟 34
第四章模擬程序驗證 37
4-1 等溫吸附實驗 37
4-1-1 實驗裝置 37
4-1-2 實驗步驟 41
4-1-3 天平校正 42
4-1-4 等溫吸附平衡曲線 43
4-2 突破曲線實驗 46
4-2-1 實驗裝置 46
4-2-2 突破實驗操作步驟 47
4-3 模擬驗證 48
4-4 單塔四步驟實驗與模擬驗證 50
第五章甲烷重組氣多塔模擬 54
5-1 吸附劑能力及吸附劑選擇 54
5-2 兩塔六步驟模擬程序及模擬參數介紹 57
5-2-1 雙塔六步驟模擬結果 60
5-3 三塔九步驟模擬程序 62
5-3-1 程序介紹 62
5-3-2 三塔九步驟模擬結果 64
5-3-3 以實驗設計求三塔九步驟最佳化操作條件結果 66
5-3-4 變異數分析及因子探討 67
5-3-5 實驗設計最佳化結果與比較 72
5-4 三塔十五步驟模擬結果 73
5-4-1 程序介紹 73
5-4-2 三塔十五步驟模擬結果 75
5-4-3 以實驗設計求三塔十五步驟最佳化操作條件結果 76
5-4-4 變異數分析及因子探討 77
5-4-5 實驗設計最佳化結果與比較 84
5-5 能耗討論 85
5-5-1 能耗計算公式 85
5-5-2 能耗計算之結果 86
第六章結論 87
符號說明 89
附錄A、流速之估算方法 93
參考資料 96

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指導教授

周正堂(Cheng-Tung Chou)

審核日期

2023-7-24

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