利用雙塔變壓吸附程序濃縮及回收氣化產氫製程中之二氧化碳與氫氣

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姓名

李建佑(Chien-Yu Lee) 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

利用雙塔變壓吸附程序濃縮及回收氣化產氫製程中之二氧化碳與氫氣
(Using Dual-Bed PSA Process to Concentrate and Recover H2 and CO2 from Gasification Process for H2 Production)

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摘要(中)

煤炭進行水蒸氣觸媒反應後，進一步將觸媒重組物通過水煤氣轉化反應器（water gas-shift reactor）則可得到大量以氫氣、二氧化碳為主體的混合氣體（syngas）。但經由上述所得典型混合產氣，大部分氣體成分為H2、CO2及N2。因此，氫氣的純化程序為製造高純度氫氣（99%+)不可或缺的步驟。
本研究便以合成氣的組成為目標，以實驗探討使用變壓吸附製程純化合成氣中二氧化碳與氫氣的最佳操作條件。
實驗主要分為二階段，以雙塔四步驟真空變壓吸附（4 steps vacuum swing adsorption）製程，來進行操作變數對製程影響的探討。
第一階段為CO2-VSA （vacuum swing adsorption），主要為回收合成氣中之CO2，吸附劑採用zeolite 13X，進料組成為模擬合成氣，訂為40% H2、50% CO2、10% N2；第二階段為H2-VSA，主要再純化第一階段之弱吸附出氣（塔頂出氣），吸附劑採用activated carbon及zeolite 5A混合填塔，進料組成為第一階段CO2-VSA之塔頂出氣組成，訂為60% H2、23.4% CO2、16.6% N2。
實驗上藉由改變操作變數，如：進料壓力、步驟時間、活性碳長度比（carbon ratio ,c.r.）等，以得到最佳的分離操作條件。
結果，可在第一階段CO2-VSA將CO2濃度達到99%（回收率59%）；第二階段H2-VSA將H2 濃度達到95%（回收率44%）。

摘要(英)

The gas from coal, then passing through the water gas-shift reactor,will get a large mount gas mixture (syngas) with main components H2, CO2 and N2. For this reason, it is necessary to have a purification process to manufacture high purity (99%+) hydrogen.
This study experimental study the use of PSA (pressure swing adsorption) process to purify the CO2 and H2 in syngas.
The process includes two stages,which uses the two bed 4-steps vacuum swing adsorption process,to study the effects of the operating parameter on the system.
Stage 1 is the CO2-VSA (vacuum swing adsorption), mainly separating the CO2 of syngas. The adsorbent is zeolite 13X. Feed gas mixture contains 40% H2, 50% CO2, and 10% N2, which simulats the syngas composition. Stage 2 is the H2-VSA, mainly purifying the weak adsorbed component gas (mainly H2) from the bed top of the stage 1. The adsorbents include activated carbon and zeolite 5A in a layered bed. Feed gas composition is the composition of the bed top gas of the stage 1, which is 60% H2, 23.4% CO2 and 16.6% N2.
The optimal operating conditions is obtained by changing the operating variables,for example,feed gas pressure,step time and carbon ratio in the bed.
For stage 1 CO2-VSA,the CO2 purity can reach 99% with a recovery of 59%； for stage 2 H2-VSA the purity can reach 95% with recovery 44%.

關鍵字(中)

★ 變壓吸附
★ 氫氣
★ 二氧化碳
★ 實驗
★ 13X沸石
★ 5A沸石
★ 活性碳
★ 層床

關鍵字(英)

★ layered bed
★ activated carbon
★ Pressure swing adsorption
★ hydrogen
★ carbon dioxide
★ experiment
★ zeolite 13X
★ zeolite 5A

論文目次

摘要 i
Abstract ii
誌謝 iii
目錄 iv
圖目錄 vi
表目錄 viii
符號說明 ix
第一章緒論 1
第二章變壓吸附簡介與文獻回顧 7
2.1 變壓吸附簡介 7
2.1.1 吸附現象簡介 7
2.1.2 吸附程序簡介 8
2.1.3 變壓吸附的基本原理 9
2.1.4 吸附劑的選擇 17
2.1.5 吸附劑的種類 25
2.1.6 變壓吸附程序的基本操作步驟 26
2.2 文獻回顧 29
2.2.1 PSA製程之發展與改進 29
2.2.2 以PSA製程回收二氧化碳的應用 30
2.2.3 以PSA製程純化氫氣的應用 33
第三章 PSA濃縮二氧化碳及氫氣的方法 36
3.1 變壓吸附實驗程序 36
3.2 實驗裝置、各部規格及特性 42
3.4 真空變壓吸附程序實驗步驟與條件 53
第四章結果與討論 57
4.1 Stage1 CO2-VSA程序之探討 59
4.1.1 Skarstrom程序下吸附劑的吸附效果比較 61
4.1.2 Skarstrom程序下變換壓力對UOP 13X-APG與UOP PSA O2 HP沸石的影響 63
4.1.3 三種不同的四步驟程序之比較 68
4.1.4 Skarstrom-Vacuum程序下變換T1時間的影響 71
4.1.5 Skarstrom-Vacuum程序下變換T2時間的影響 77
4.2 Stage 2 H2-VSA程序之探討 81
4.2.1 Skarstrom-Vacuum程序下的簡單測試 83
4.2.2 Skarstrom-Vacuum程序下變換壓力的影響 90
4.2.3 Skarstrom-Vacuum程序下變換T2時間的影響 94
4.2.4 Skarstrom-Vacuum程序下變換c.r.(carbon ratio)的影響 98
第五章結論 102
參考文獻 103
附錄A GC操作步驟 111
附錄B 可程式控制器控制與程式 113
附錄 C-1 Stage1 CO2-VSA程序各點實驗數據 123
附錄 C-2 Stage2 H2-VSA程序各點實驗數據 129
附錄 D-1 UOP MOLSIV Type 13X沸石物理參數 136
附錄 D-2 UOP 13X-APG MOLSIV沸石物理參數 137
附錄 D-4 Merck Molecule sieve 0.5nm沸石物理參數 139
附錄 D-5 Calgon AC Type BPL 4×10 granular物理參數 140
附錄 D-6 Calgon AC Type BPL 6×16 granular物理參數 141

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指導教授

周正堂(Cheng-tung Chou)

審核日期

2007-7-23

推文