利用中孔徑矽分子篩MCM-41分離、量測大氣二氧化碳

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研究生：	黃新維 Hsin-wei Huang
論文名稱：	利用中孔徑矽分子篩MCM-41分離、量測大氣二氧化碳 Using MCM-41 as a separation material for the measurements of atmospheric CO2
指導教授：	王家麟 Jia-lin Wang
口試委員:
學位類別：	碩士 Master
系所名稱：	理學院 - 化學學系 Department of Chemistry
畢業學年度：	98
語文別：	中文
論文頁數：	103
中文關鍵詞：	二氧化碳、氣相層析、MCM-41 、中孔徑矽分子篩
外文關鍵詞：	Carbon dioxide, gas chromatography, MCM-41, mesoporous silicates
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本研究中利用中孔徑矽分子篩MCM-41作為填充靜相，自製填充層析管柱，完成一自動氣相層析系統，針對大氣溫室效應氣體CO2進行大氣連續監測。系統以逆吹方式設計，在定溫下達到管柱自我清除與調適之目的。利用MCM-41其較大孔徑(46.6A)的特性，使空氣中的N2、O2、CH4與CO等小分子物種可與CO2做快速分離而流析出，而高沸點物質可在進入分析管柱前即被逆吹帶出預管柱使不致累積於分析管柱內影響層析效果。偵測方式是以自製鎳觸媒管做為甲烷轉化器，將CO2還原成為CH4，再使用火焰離子偵測器(FID)偵測之，間接測得CO2濃度。又另建置一自動進樣系統，將標準氣體以及大氣樣品的進樣動作全部自動完成，達到連續監控大氣中CO2的目的。完成後之層析系統其線性(R2)可達0.995，再現性優於1%以內，偵測下限為10 ppmv 。本方法與氣體過濾相關光度計(gas filtercorrelation photometer)進行平行比測，為期32天連續監測大氣中之CO2濃度，以驗證本方法在連續監測大氣CO2的穩定性與準確性，開啟中孔徑矽分子篩在大氣溫室效應氣體層析方面的嶄新應用。
實驗後期對MCM-41的耐久性做探討，管柱內之MCM-41雖受長時間空氣進樣時所帶入的水氣導致結塊現象而影響到層析的穩定性，但經過XRD鑑定後其多孔結構在使用前後無顯著差異，可知MCM-41的多孔結構具有良好的穩定性。再利用商業材料Hayesep Q填充管柱與MCM-41管柱比較之，發現CO2峰之滯留時間仍有小幅度之變動(RSD = 0.41%)，且感度存在一微幅之上升趨勢，顯示觸媒轉換效率無法維持長期穩定，需藉由定期打入標準氣體以校正此系統性之偏差。

In this study, mesoporous silicate MCM-41 was used as the stationary
phase of a packed column in an back-flushed automated gas chromatographic system for analyzing atmospheric CO2. Because of the larger pore size (46.6A) of MCM-41, smaller molecules in air like N2, O2, CH4, and CO combined can be rapidly separated from CO2. The backflush chromatographic design allowed column self-cleaning and conditioning, which is curtail for long-term continuous operation. For detection CO2 was reduced into CH4 by a methanizer using Ni as the catalyst kept at 375℃. Methane detected by flame ionization detection (FID) was proportional to atmospheric CO2 concentration. Sample injection was performed by a pressure setpoint of 700 torr in a 0.81mL sample loop with a precision (RSD) of 0.049%, and can be switched between ambient air and standard gas. The linearity (R2) was better than 0.995, the reproducibility was within 1%, and the detection limit was 10 ppmv. The GC system was intercompared with a gas filter correlation (GFC) photometer for continuous monitoring atmospheric CO2 for a period of 32 days. Comparable results were observed with CO2 concentration varied between 334.1 and 681.4 ppmv with a mean value of 409.9 ppmv. The agreement can be revealed by a correlation coefficient of 0.82 between the two methods. The success in the use of mesoporous silicates for chromatographic analysis of CO2 opened new room for greenhouse gas monitoring.
In later study, the durability of MCM-41 was examined by unpacking
MCM-41 from the column after prolonged use. Although agglomeration of
MCM-41 particles by water vapor in air sample aliquots was observed, which
somewhat affected the peak retention time, powered X-ray analysis suggested that the integrity of the porosity still remained intact. A commercial packing material Hayesep Q was further compared with MCM-41 to verify the system stability. It was found that the slight increasing trend in sensitivity was likely due to the slow degradation of Ni catalyst overtime, which can be overcome and corrected by daily calibration.

摘 要.....................................................................................................I
Abstract ............................................................................................................ III
謝 誌...................................................................................................V
目 錄.............................................................................................. VIII
圖 目 錄..................................................................................................XI
表 目 錄...............................................................................................XIV
第一章、前言.................................................................................................... 1
1-1 研究緣起..................................................................................................1
1-2 CO2分析方法與文獻回顧......................................................................3
1-2-1 氣相層析儀/火焰離子偵測器............................................................ 5
1-2-2 非分散式紅外光吸收法...................................................................10
1-2-3 腔體震盪光譜法...............................................................................15
1-3 全球量測現況.......................................................................................18
1-4 中孔徑分子篩.......................................................................................22
1-4-1 簡介...................................................................................................22
1-4-2 合成機制...........................................................................................24
1-4-3 MCM-41應用.....................................................................................28
1-5 研究動機................................................................................................30
二、實驗方法.................................................................................................. 31
2-1 器材與試劑............................................................................................31
2-1-1 實驗藥品...........................................................................................31
2-1-2 實驗器材...........................................................................................33
2-2 系統設計................................................................................................34
2-2-2 進樣壓力控制...................................................................................37
2-2-3 自動化標準品進樣方法...................................................................41
2-3 層析管柱選擇.......................................................................................45
2-4 鎳觸媒甲烷化裝置...............................................................................47
2-5 逆吹系統................................................................................................52
三、結果與討論.............................................................................................. 55
3-1 甲烷轉化器溫度...................................................................................55
3-2 MCM-41層析管柱定性.........................................................................57
3-3 實測測量................................................................................................59
3-3-1 分析條件...........................................................................................59
3-3-2 樣品殘留...........................................................................................60
3-3-3 工作標準品校正...............................................................................63
3-3-4 再現性與線性表現...........................................................................65
3-3-5 實測...................................................................................................67
3-4 層析條件變化.......................................................................................72
3-4-1 圖譜飄移...........................................................................................72
3-4-2 靜相變質...........................................................................................73
3-4-3 MCM-41結構.....................................................................................77
3-5 問題查證................................................................................................80
3-5-1 實驗條件...........................................................................................80
3-5-2 甲烷分析...........................................................................................81
3-5-3 層析圖譜...........................................................................................83
3-5-4 系統穩定度.......................................................................................86
第四章、結論與未來展望............................................................................. 90
第五章、參考文獻.......................................................................................... 92
附錄一 安捷倫軟體Chemstation批次檔使用............................................ 98

                                

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